Back to EveryPatent.com
| United States Patent |
5,573,898
|
|
Sakai
|
November 12, 1996
|
Silver halide color photographic material
Abstract
Disclosed is a silver halide color photographic material having plural
light-sensitive layers on a reflective support, in which the reflective
support is composed of a base and two or more waterproof resin coat layers
each having a different white pigment content in such a way that the resin
coat layers are sandwiched between the base and the light-sensitive
layers, the cyan coupler-containing silver halide emulsion layer contains
a particular pyrroloazole cyan dye-forming coupler, and the pH of the
coated film of the material is from 4.0 to 6.5. The material is low-priced
and has a good coloring property, excellent color reproducibility and high
sharpness. As the material has sufficient pressure resistance, it has few
stress marks even after stored. Also disclosed is a method for forming a
color image, using the photographic material.
| Inventors:
|
Sakai; Hidekazu (Kanagawa, JP)
|
| Assignee:
|
Fuji Photo Film Co., Ltd. (Kanagawa, JP)
|
| Appl. No.:
|
313587 |
| Filed:
|
September 29, 1994 |
Foreign Application Priority Data
| Current U.S. Class: |
430/503; 430/531; 430/533; 430/538; 430/551; 430/558 |
| Intern'l Class: |
G03C 001/46 |
| Field of Search: |
430/531,533,538,551,503,558,384,385,505
|
References Cited
U.S. Patent Documents
| 5024932 | Jun., 1991 | Tanji et al. | 430/567.
|
| 5256526 | Oct., 1993 | Suzuki et al. | 430/384.
|
| 5270153 | Dec., 1993 | Suzuki et al. | 430/384.
|
| 5342747 | Aug., 1994 | Morigaki et al. | 430/551.
|
| 5364748 | Nov., 1994 | Yoneyama | 430/505.
|
| 5429916 | Jul., 1995 | Ohshima | 430/538.
|
| Foreign Patent Documents |
| 4-256948 | Sep., 1992 | JP.
| |
Primary Examiner: Letscher; Geraldine
Attorney, Agent or Firm: Birch, Stewart, Kolasch & Birch, LLP
Claims
What is claimed is:
1. A silver halide color photographic material having, on a reflective
support, at least one yellow dye-forming coupler-containing silver halide
emulsion layer, at least one magenta dye-forming coupler-containing silver
halide emulsion layer and at least one cyan dye-forming coupler-containing
silver halide emulsion layer each having a different color sensitivity,
wherein said reflective support is composed of a base and two or more
waterproof resin coat layers each having a different white pigment
content, the resin coat layers being provided on the surface side of the
base where the silver halide emulsion layers are coated thereover, the
waterproof resin coat layer that is nearest to the base having a lower
white pigment content than at least one of the waterproof resin coat
layers positioned farther from the base;
wherein said yellow dye-forming coupler-containing silver halide emulsion
layer is adjacent to the waterproof resin coat layer that is farthest away
from said base; said cyan dye-forming coupler-containing silver halide
emulsion layer contains at least one cyan dye-forming coupler compound of
the following general formula (Ia); and the coated layers of the
photographic material, combined, have a pH that falls within the range of
from 4.0 to 6.5:
##STR125##
wherein Za represents --NH-- or --CH(R.sub.3)--; Zb and Zc each represent
--C(R.sub.4).dbd. or --N.dbd.;
R.sub.1, R.sub.2 and R.sub.3 each represent an electron-attracting group
having a Hammett's substituent constant .sigma.p of 0.20 or more, provided
that the sum of the .sigma.p values of R.sub.1 and R.sub.2 is 0.65 or
more;
R.sub.4 represents a hydrogen atom, a halogen atom, an aliphatic group, an
aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a
heterocyclic-oxy group, an alkyl-, aryl- or heterocyclic-thio group, an
acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy
group, an acylamino group, an alkylamino group, an arylamino group, an
ureido group, a sulfamoylamino group, an alkenyloxy group, a formyl group,
an alkyl-, an aryl- or heterocyclic-acyl group, an alkyl-, aryl- or
heterocyclic-sulfonyl group, an alkyl-, aryl- or heterocyclic-sulfinyl
group, an alkyl-, aryl- or heterocyclic-oxycarbonyl group, an alkyl-,
aryl- or heterocyclic-oxycarbonylamino group, a sulfonamido group, a
carbamoyl group, a sulfamoyl group, a phosphonyl group, a sulfamido group,
an imido group, a hydroxyl group, a cyano group, a carboxyl group, a nitro
group, a sulfo group or an unsubstituted amino group, provided that when
the formula has two R.sub.4 's, they are the same or different;
X represents a hydrogen atom or a group capable of splitting off from the
compound by the coupling reaction with an oxidation product of an aromatic
primary amine color developing agent; and
when R.sub.1, R.sub.2, R.sub.3, R.sub.4 or X is a divalent group, the
compound may be a dimer or a higher polymer, or the divalent group may be
bonded to a polymer chain to form a homopolymer or copolymer.
2. The silver halide color photographic material as claimed in claim 1, in
which the cyan dye-forming coupler compound of formula (Ia) is selected
from the group consisting of cyan dye-forming coupler compounds of general
formulae (IIa) to (VIIIa):
##STR126##
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 or X have the same meanings as
those in formula (Ia).
3. The silver halide color photographic material as claimed in claim 1, in
which the cyan dye-forming coupler compound of formula (Ia) is a cyan
dye-forming coupler compound of a general formula (Ib):
##STR127##
wherein R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9 each independently
represent a hydrogen atom, a halogen atom, an aliphatic group, an aryl
group, a heterocyclic group, an alkoxy group, an aryloxy group, a
heterocyclic-oxy group, an alkyl-, aryl- or heterocyclic-thio group, an
acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy
group, an acylamino group, an alkylamino group, an arylamino group, an
ureido group, a sulfamoylamino group, an alkenyloxy group, a formyl group,
an alkyl-, an aryl- or heterocyclic-acyl group, an alkyl-, aryl- or
heterocyclic-sulfonyl group, an alkyl-, aryl- or heterocyclic-sulfinyl
group, an alkyl-, aryl- or heterocyclic-oxycarbonyl group, an alkyl-,
aryl- or heterocyclic-oxycarbonylamino group, a sulfonamido group, a
carbamoyl group, a sulfamoyl group, a phosphonyl group, a sulfamido group,
an imido group, a hydroxyl group, a cyano group, a carboxyl group, a nitro
group, a sulfo group or an unsubstituted amino group;
Z represents a non-metallic atomic group necessary for forming a
substituted or unsubstituted ring, said ring substituents being selected
from the group consisting of a halogen atom, an aliphatic group, an aryl
group, a heterocyclic group, an alkoxy group, an aryloxy group, a
heterocyclic-oxy group, an alkyl-, aryl- or heterocyclic-thio group, an
acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy
group, an acylamino group, an alkylamino group, an arylamino group, an
ureido group, a sulfamoylamino group, an alkenyloxy group, a formyl group,
an alkyl-, an aryl- or heterocyclic-acyl group, an alkyl-, aryl- or
heterocyclic-sulfonyl group, an alkyl-, aryl- or heterocyclic-sulfinyl
group, an alkyl-, aryl- or heterocyclic-oxycarbonyl group, an alkyl-,
aryl- or heterocyclic-oxycarbonylamino group, a sulfonamido group, a
carbamoyl group, a sulfamoyl group, a phosphonyl group, a sulfamido group,
an imido group, a hydroxyl group, a cyano group, a carboxyl group, a nitro
group, a sulfo group or an unsubstituted amino group; provided that when
the ring is an aromatic ring or an aromatic heterocyclic ring, the formula
does not have R.sub.7, R.sub.8 and R.sub.9 ;
R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9 and the substituent(s), if
any, on Z may be bonded to each other to form ring(s); and
R.sub.4 and X have the same meanings as those in formula (Ia).
4. The silver halide color photographic material as claimed in claim 1, in
which, in the reflective support composed of a base and two or more
waterproof resin coat layers each having a different white pigment
content, the waterproof resin coat layer that is nearest to the silver
halide emulsion layers has the highest white pigment content.
5. The silver halide color photographic material as claimed in claim 1, in
which the reflective support has, on the base, at least three or more
waterproof resin coat layers each having a different white pigment
content; a waterproof resin coat layer located between the waterproof
resin coat layer nearest to the silver halide emulsion layers and the
waterproof resin coat layer nearest to the base has the highest white
pigment content.
6. The silver halide color photographic material as claimed in claim 1, in
which the white pigment in the waterproof resin coat layers constituting
the reflective support is titanium dioxide and the ratio by weight of the
white pigment to the resin is 15/85 (titanium dioxide/resin) or more in
the waterproof resin coat layer having the highest white pigment content.
7. The silver halide color photographic material as claimed in claim 1, in
which said cyan dye-forming coupler-containing silver halide emulsion
layer contains at least one compound selected from the group consisting of
oleophilic compounds of the following general formulae (A), (B) and (C),
that chemically bond to an aromatic primary amine color developing agent
under the condition of pH 8 or less to give substantially colorless
products, and oleophilic compounds of the following general formula (D)
that chemically bond to an oxidation product of an aromatic primary amine
color developing agent under the condition of pH 8 or less to give
substantially colorless products:
##STR128##
wherein, in formula (A), L.sub.a1 represents a single bond, --O--, --S--,
--CO-- or --N(R.sub.a2)--, wherein R.sub.a2 represents an aliphatic group,
an aromatic group, a heterocyclic group, a hydrogen atom, an acyl group, a
sulfonyl group, a carbamoyl group or a sulfamoyl group; R.sub.a1
represents an aliphatic group, an aromatic group, or a heterocyclic group;
Z.sub.a1 represents an oxygen atom or a sulfur atom; Z.sub.a2 represents a
hydrogen atom, --O--R.sub.a3, --S--R.sub.a4, --L.sub.a2 --C(.dbd.Z.sub.a1
')R.sub.a5, or a heterocyclic group bonding to the formula via a nitrogen
atom; R.sub.a3 and R.sub.a4 are the same or different and each represents
a vinyl group, an aromatic group or a heterocyclic group; L.sub.a2
represents --O-- or --S--; Z.sub.a1 ' has the same meaning as Z.sub.a1 ;
R.sub.a5 represents an aliphatic group, an aromatic group or a
heterocyclic group; alternatively, at least two of R.sub.a1, R.sub.a2 and
Z.sub.a2 are bonded to each other to form a 5-membered to 7-membered ring;
in formula (B), R.sub.b1 represents an aliphatic group; and Z.sub.b1
represents a halogen atom;
in formula (C), Z.sub.c1 represents a cyano group, an acyl group, a formyl
group, an aliphatic-oxycarbonyl group, an aromatic-oxycarbonyl group, a
carbamoyl group, a sulfamoyl group, or a sulfonyl group; R.sub.c1,
R.sub.c2 and R.sub.c3 are the same or different and each represents a
hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group
or Z.sub.c1 ; alternatively at least two of R.sub.c1, R.sub.c2, R.sub.c3
and Z.sub.c1 are bonded to each other to form a 5-membered to 7-membered
ring;
in formula (D), R.sub.d1 represents an aliphatic group or an aromatic
group; Z.sub.d1 represents a mercapto group or --SO.sub.2 Y, wherein Y
represents a hydrogen atom, an atom or atomic group for forming an
inorganic or organic salt, --NHN.dbd.C(R.sub.d2)R.sub.d3,
--N(R.sub.d4)--N(R.sub.d5)--SO.sub.2 R.sub.d6,
--N(R.sub.d7)--N(R.sub.d8)--COR.sub.d9 or
--C(R.sub.d10)(OR.sub.d11)--COR.sub.d12 ; R.sub.d2 and R.sub.d3 are the
same or different and each represents a hydrogen atom, an aliphatic group,
an aromatic group or a heterocyclic group; alternatively R.sub.d2 and
R.sub.d3 are bonded to each other to form a 5-membered to 7-membered ring;
R.sub.d4, R.sub.d5, R.sub.d7 and R.sub.d8 are the same or different and
each represents a hydrogen atom, an aliphatic group, an aromatic group, a
heterocyclic group, an acyl group, an aliphatic-oxycarbonyl group, a
sulfonyl group, an ureido group or an urethane group, provided that at
least one of R.sub.d4 and R.sub.d5 and at least one of R.sub.d7 and
R.sub.d8 are hydrogen atoms; R.sub.d6 represents a hydrogen atom, an
aliphatic group, an aromatic group, a heterocyclic group, an aliphatic
amino group, an aromatic amino group, an aliphatic-oxy group, an
aromatic-oxy group, an acyl group, an aliphatic-oxycarbonyl group or an
aromatic-oxycarbonyl group; R.sub.d9 represents a hydrogen atom, an
aliphatic group, an aromatic group, or a heterocyclic group; alternatively
at least two of R.sub.d4, R.sub.d5 and R.sub.d6 are bonded to each other
to form a 5-membered to 7-membered ring, or at least two of R.sub.d7,
R.sub.d8 and R.sub.d9 are bonded to each other to form a 5-membered to
7-membered ring; R.sub.d12 represents a hydrogen atom, an aliphatic group,
an aromatic group or a heterocyclic group; R.sub.d10 represents a hydrogen
atom, an aliphatic group, an aromatic group, a halogen atom, an acyloxy
group, or a sulfonyl group; and R.sub.d11 represents a hydrogen atom or a
hydrolyzable group.
8. The silver halide color photographic material as claimed in claim 7, in
which said compounds of formula (A) are selected from the group consisting
of compounds represented by one of the following formula (A-I) to (A-V):
##STR129##
wherein in formulae (A-I) to (A-V), R.sub.e1 has the same meaning as
R.sub.a1 in formula (A); L.sub.e1 represents a single bond or --O--;
L.sub.e2 represents --O-- or --S--; Ar represents an aromatic group;
R.sub.e2 to R.sub.e4 are the same or different and each represents a
hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic
group, an aliphatic-oxy group, an aromatic-oxy group, a heterocyclic-oxy
group, an aliphatic-thio group, an aromatic-thio group, a
heterocyclic-thio group, an amino group, an aliphatic amino group, an
aromatic amino group, a heterocyclic amino group, an acyl group, an amido
group, a sulfonamido group, a sulfonyl group, an aliphatic-oxycarbonyl
group, an aromatic-oxycarbonyl group, a sulfo group, a carboxyl group, a
formyl group, a hydroxyl group, an acyloxy group, an ureido group, an
urethane group, a carbamoyl group or a sulfamoyl group; alternatively at
least two of R.sub.e2 to R.sub.e4 are bonded to each other to form a
5-membered to 7-membered ring; Z.sub.e1 and Z.sub.e2 each represent a
non-metallic atomic group necessary for forming a 5-membered to 7-membered
ring; Z.sub.e3 represents a non-metallic atomic group necessary for
forming a 5-membered to 7-membered aromatic ring.
9. The silver halide color photographic material as claimed in claim 8,
wherein said oleophilic compound is a compound of fomula (A-I) or (A-III)
and is selected from the group consisting of:
##STR130##
10. The silver halide color photographic material as claimed in claim 7,
wherein Y represents an inorganic or organic salt that is selected from
the group consisting of Li, Na, K, Ca, Mg, triethylamine, methylamine, and
ammonia.
11. The silver halide color photographic material as claimed in claim 7,
wherein R.sub.d11 represents a hydrolyzable group that is selected from
the group consisting of an acyl group, a sulfonyl group, an oxalyl group,
and a silyl group.
12. The silver halide color photographic material as claimed in claim 1,
wherein the silver halide grains are silver chlorobromide or silver
chloroiodobromide grains, each having at least 95 mol % silver chloride,
or silver chloride grains.
13. The silver halide color photographic material, as claimed in claim 1,
wherein said pH is in the range of from 5.0 to 6.0.
Description
FIELD OF THE INVENTION
The present invention relates to a color photographic material and to a
method for forming a color image using the material. More precisely, it
relates to a color photographic material which has a good coloring
property with excellent color reproducibility and sharpness, which is
low-priced and which is resistant to pressure causing stress marks when
stored, and to a method for forming a color image using the material.
BACKGROUND OF THE INVENTION
Color photographs which have been widely popularized in these days have
much improved to be easily and rapidly available anywhere due to the
improvement in photographic materials themselves and developing and
processing techniques. For color printing papers to be used to produce
viewing color prints, in particular, the realization of photographic
materials containing high silver chloride emulsions has brought about
highly-rapid processing of the materials. The market where highly-rapid
processing of photographic materials is being promoted needs the
improvement in the sharpness and the color reproducibility of photographic
materials to give high-quality photographic images and, in addition,
further needs the provision of such high-quality photographic products at
low costs.
The color image forming method which is most generally employed in
processing silver halide color photographic materials is such that the
exposed silver halides in the material are reacted with, as the oxidizing
agent, an oxidized, aromatic primary amine color developing agent to form
indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and
the like dyes. According to the method, employed is subtractive color
photography to reproduce color images. In general, color images are formed
by varying the amounts of three dyes comprised of yellow, magenta and cyan
dyes to be formed in the processed photographic material.
To form cyan color images, generally used are phenol or naphthol cyan
couplers. However, since these couplers have unfavorable absorption in the
green light range and the blue light range, these have a serious problem
in that they noticeably worsen the blue and green color reproducibility.
Therefore, it is strongly desired to solve the problem.
As one means for solving the problem, it has been proposed to employ
2,4-diphenylimidazole cyan couplers. The dyes to be formed from these
couplers have more reduced unfavorable absorption in the green and blue
ranges than those to be formed from conventional couplers, and the color
reproducibility of these couplers has surely been improved in some degree.
However, it is difficult to say that the color reproducibility of these
couplers is satisfactory and further improvement in their color
reproducibility is desired. In particular, these couplers have serious
problems in that their reactivity with oxidation products of developing
agents or, that is, their coupling activity is low and that the heat
resistance and the light fastness of the dyes to be formed from these
couplers are extremely low. For these reasons, these couplers cannot be
put to practical use.
Pyrazoloazole cyan couplers are better than conventional cyan couplers in
that the unfavorable absorption of the dyes to be formed from the
pyrazoloazole cyan couplers in the green and blue ranges is less than that
of the dyes to be formed from the conventional cyan couplers, but the
pyrazoloazole cyan couplers still have problems in that their color
reproducibility is not satisfactory and that their coloring property is
extremely bad.
As couplers of forming dyes with excellent color hue, pyrrolopyrazole cyan
couplers are known. These couplers are better than the above-mentioned
pyrazoloazole cyan couplers with respect to their color reproducibility
but are not still satisfactory. They have a drawback in that they give
much color fog in the non-exposed area. In addition, their coloring
property is not still in a satisfactory level.
As cyan couplers which are free from the above-mentioned problems or, that
is, those having a good coloring property and giving dyes with reduced
unfavorable absorption in the green and blue ranges, European Patents
0,491,197 and 0,488,248 have proposed pyrroloazole cyan couplers having
particular substituents. These cyan couplers form dyes having an excellent
absorbing characteristic or, that is, dyes having a large molar extinction
coefficient and having a sharp spectral profile in the short wavelength
range (characterized in that the unfavorable absorption in the green range
and the blue range has been reduced), and their coloring property or, that
is, their reactivity with oxidation products of developing agents is high
while the heat resistance and the light fastness of the dyes to be formed
from them are excellently high. From these viewpoints, the cyan couplers
are favorable.
On the other hand, the support in color printing papers is designed in such
a way that the base of the support is coated with a polyolefin layer
containing titanium dioxide that has been kneaded and dispersed thereinto,
on its surface side where photographic emulsions are to be coated
thereover, in order to improve its water-proofness and its light
reflectivity. Various means have heretofore been known to improve the
sharpness of silver halide photographic materials having such a reflective
support. Such means include, for example, (1) anti-irradiation by the use
of water-soluble dyes, (2) anti-halation by the use of colloidal silvers,
mordant dyes, fine grains of solid dyes, etc., (3) protection of the
support from light by increasing the amount of the white pigment to be in
the laminate resin on a paper support or by additionally coating a gelatin
dispersion of a white pigment on the support, etc.
Of these means, however, (1) and (2) have serious problems in that they
result in noticeable decrease in the sensitivity of photographic materials
and result in increase in the color stains in the processed photographic
materials. According to the means (3), the sharpness of photographic
materials may be improved noticeably by coating a gelatin dispersion
containing a white pigment on the support, but the coating of the white
pigment-containing gelatin dispersion worsens the storability of
non-exposed photographic materials and increases the total thickness of
photographic materials, thereby causing various new problems in that the
stability of photographic materials during their processing is lowered,
the drying speed thereof is lowered so that the materials are not
applicable to rapid processing, the production costs of the materials are
elevated, etc.
On the other hand, it is known that the sharpness of photographic materials
may be remarkably improved by increasing the content of the white pigment
in the polyolefin laminate on the support. However, such increase results
in the elevation of the production costs of photographic materials so that
it is impracticable. JP-A 49-30446, 2-58042, 1-142549, 4-256947, 4-256948,
etc. have disclosed reflective supports having two or more polyolefin
layers having different white pigment contents. (The term "JP-A" as used
herein means an "unexamined published Japanese patent application".)
According to these constitutions, it has been known that the amount of the
white pigment to be used may be reduced while the sharpness of
photographic materials is kept high and therefore the proposed
constitutions are advantageous in view of the production costs.
However, it has been found that when pressure is applied to a photographic
material having a support comprising such a multi-layered resin layer
before its development, the area of the material to which pressure was
applied is fogged during its processing or, that is, the processed
material is to have stress marks around the area. This problem is not so
significant when the photographic material contains conventional phenol or
naphthol cyan couplers, but is serious when the material contains cyan
couplers of a general formula (Ia) which will be mentioned hereinafter so
as to have an improved coloring property and improved color
reproducibility. In addition, it has been found that the above-mentioned
stress marks appear noticeably in stored photographic materials though
appearing in some degree in fresh photographic materials. Moreover, it has
been found that this problem is more serious in silver halide emulsion
grains having an extremely high silver chloride content.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a color photographic
material which has a good coloring property with excellent color
reproducibility and sharpness, which is low-priced and which is resistant
to pressure causing stress marks when stored, and also to provide a method
for forming a color image using the material.
The present inventor assiduously studied so as to solve the above-mentioned
problems and to attain the above-mentioned object and, as a result, has
found that the problems may be solved and the object may be attained by a
silver halide color photographic material having, on a reflective support,
at least one yellow dye-forming coupler-containing silver halide emulsion
layer, at least one magenta dye-forming coupler-containing silver halide
emulsion layer and at least one cyan dye-forming coupler-containing silver
halide emulsion layer each having a different color sensitivity, which is
characterized in that said reflective support is composed of a base and
two or more waterproof resin coat layers each having a different white
pigment content, the resin coat layers being provided on the surface side
of the base where the silver halide emulsion layers are coated thereover,
that said cyan dye-forming coupler-containing silver halide emulsion layer
contains at least one cyan dye-forming coupler compound of the following
general formula (Ia) and that the pH of the coated film of the
photographic material falls within the range of from 4.0 to 6.5.
##STR1##
wherein Za represents --NH-- or --CH(R.sub.3)--;
Zb and Zc each represent --C(R4).dbd. or --N.dbd.;
R.sub.1, R.sub.2 and R.sub.3 each represent an electron-attracting group
having a Hammett's substituent constant .sigma.p of 0.20 or more, provided
that the sum of the .sigma.p values of R.sub.1 and R.sub.2 is 0.65 or
more;
R.sub.4 represents a hydrogen atom or a substituent, provided that when the
formula has two R.sub.4 's, they may be the same or different;
X represents a hydrogen atom or a group capable of splitting off from the
compound by the coupling reaction with an oxidation product of an aromatic
primary amine color developing agent; and
when R.sub.1, R.sub.2, R.sub.3, R.sub.4 or X is a divalent group, the
compound may be a dimer or a higher polymer, or the divalent group may be
bonded to a polymer chain to form a homopolymer or copolymer.
As one embodiment of the present invention, the cyan dye-forming coupler of
formula (Ia) in the silver halide color photographic material is a cyan
dye-forming coupler represented by a general formula (Ib):
##STR2##
wherein R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9 each represent a
hydrogen atom or a substituent;
Z represents a non-metallic atomic group necessary for forming a ring,
which may optionally be substituent(s), the ring to be formed by Z may be
an aromatic ring or a heterocyclic ring, but when the ring is an aromatic
ring or an aromatic heterocyclic ring, the formula does not have R.sub.7,
R.sub.8 and Rg;
R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9 and the substituent(s), if any,
on Z may be bonded to each other to form ring(s); and
R.sub.4 and X have the same meanings as those in formula (Ia).
As another embodiment of the present invention, of the two or more of the
waterproof resin coat layer each having a different white pigment content,
one of the layers that is nearest to the base has a lower white pigment
content than at least one of the upper positioned water proof resin coat
layers.
As still another embodiment of the present invention, the waterproof resin
coat layer that is nearest to the light-sensitive layers has a highest
white pigment content.
As still another embodiment of the present invention, the reflective
support has, on the base, at least three or more waterproof resin coat
layers each having a different white pigment content in such a way that
the interlayer between the layer nearest to the light-sensitive layers and
the layer nearest to the base has a highest white pigment content.
As still another embodiment of the present invention, the white pigment in
the waterproof resin coat layers constituting the reflective support is
titanium dioxide and the ratio by weight of the white pigment to the resin
is 15/85 (titanium dioxide/resin) or more in the waterproof resin coat
layer having the highest white pigment content.
As still another embodiment of the present invention, the silver halide
color photographic material is exposed by scanning exposure for a period
of time shorter than 10.sup.-4 second per one pixcel, and thereafter the
thus-exposed material is processed for color development to form a color
image.
According to the present invention characterized in that the support has
two or more waterproof resin coat layers, that the material contains at
least one cyan coupler of formula (Ia) and that the film coated on the
material has pH of from 4.0 to 6.5, the stress marks increased by the
combination of the support having plural resin coat layers each having a
different white pigment content and the cyan coupler of formula (Ia) may
be inhibited and a photographic material having good sharpness, coloring
property and color reproducibility and a method for forming a color image
using the material may be obtained. In addition, the photographic material
of the present invention having the support having two or more waterproof
resin coat layers may have much more improved sharpness than conventional
photographic materials, even though the content of the white pigment to be
in the support of the present invention is the same as that to be added to
the conventional support so as to improve the sharpness of the
photographic material having it. In particular, the support of the present
invention having three or more resin coat layers gives a more favorable
result, when the coat layers each have a different white pigment content
and the interlayer of these has a highest white pigment content.
The support of the present invention having plural waterproof resin coat
layers each having a different white pigment content gives sharpness of
the same degree comparable to that attainable by a support having one
waterproof resin coat layer or a support having plural waterproof resin
coat layers all having the same white pigment content, even when the total
content of the white pigment in the former is less than that in the
latter.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be explained in detail hereunder.
The waterproof resin to be used in preparing the reflective support of the
present invention includes polyolefins such as polyethylene,
polypropylene, polyethylenic polymers, etc. It is especially preferably
polyethylene. As polyethylene, usable are high-density polyethylene,
low-density polyethylene, linear low-density polyethylene and polyethylene
blends of them. Before being processed, the polyolefin resin is desired to
have a melt flow rate (hereinafter referred to as MFR) falling within the
range of from 1.2 g/10 min to 12 g/10 min, in terms of the value measured
according to JIS K 7210 (Table 1, Condition 4). MFR of the non-processed
polyolefin resin as referred to herein indicates MFR of the same resin not
blended with a bluing agent and a white pigment and MFR of the same resin
not blended with a diluting resin.
The white pigment to be added to and dispersed in the waterproof resin of
the reflective support of the present invention includes, for example,
inorganic pigments such as titanium dioxide, barium sulfate, lithopone,
aluminium oxide, calcium carbonate, silicon oxide, antimony trioxide,
titanium phosphate, zinc oxide, white lead, zirconium oxide, etc., and
fine powders of organic substances such as polystyrene,
styrene-divinylbenzene copolymer, etc.
Of these pigments, titanium dioxide is especially effective. As titanium
dioxide, usable is either rutile-type or anatase-type one. However, if the
photographic material is intended to preferentially have a high level of
whiteness, anatase-type titanium dioxide is preferred, but if it is
intended to preferentially have a high level of sharpness, rutile-type
titanium dioxide is preferred. Considering both the whiteness and the
sharpness, a blend comprising anatase-type titanium dioxide and
rutile-type titanium dioxide may be used. It is also preferred to
incorporate anatase-type titanium dioxide into one or more of the
waterproof resin coat layers constituting the multi-layer support while
incorporating rutile-type titanium dioxide into the other(s) of them.
Titanium dioxide of these types may be produced by any of a sulfate method
and a chloride method. As commercial products of such titanium dioxide,
mentioned are KA-10 and KA-20 of Titanium Industrial Co., A-220 of
Ishihara Sangyo KK, etc.
The surfaces of titanium dioxide grains to be used in the present invention
may be processed with inorganic substances such as aluminium hydroxide,
silicon hydroxide, etc., or organic substances such as polyalcohols,
polyamines, metallic soap, alkyl titanates, polysiloxanes, etc., or
mixtures of such inorganic and organic substances, so as to retard the
activity of titanium dioxide and to prevent it from yellowing. The amount
of the surface-treating agent to be applied to titanium dioxide is
preferably from 0.2% by weight to 2.0% by weight for the inorganic
substances and from 0.1% by weight to 1.0% by weight for the organic
substances.
The mean grain size of titanium dioxide grains to be used in the present
invention is preferably from 0.1 to 0.8 .mu.m. If it is less than 0.1
.mu.m, the grains are difficult to uniformly mix and disperse in resins
and therefor such fine grains are unfavorable. If, however, it is more
than 0.8 .mu.m, the photographic material cannot have a sufficient degree
of whiteness and, in addition, such large grains will make small hills on
the coated surface to have a bad influence on the image quality of images
to be formed.
It is indispensable that the reflective support to be used in the present
invention has two or more waterproof resin coat layers on its surface to
be coated with light-sensitive layers and that the plural waterproof resin
coat layers each have a different white pigment content. One preferred
embodiment of the reflective support for use in the present invention is
such that the waterproof resin coat layer nearest to the base of the
support has a lower white pigment content than at least one of the upper
positioned waterproof resin coat layer. A more preferred embodiment of the
reflective support for use in the present invention is such that the
waterproof resin coat layer nearest to the light-sensitive layers has a
highest white pigment content. Another more preferred embodiment of the
reflective support for use in the present invention has at least three
waterproof resin coat layers in such a way that the interlayer between
them has a highest white pigment content. The number of the waterproof
resin coat layers each having a different white pigment content is
preferably from 2 to 7, more preferably from 2 to 5, most preferably from
3 to 5.
The white pigment content in each of these plural waterproof resin coat
layers may be from 0% by weight to 45% by weight, preferably from 0% by
weight to 40% by weight, relative to the total weight of the white pigment
and the resin of being 100% by weight. The white pigment content in the
waterproof resin coat layer having a highest white pigment content may be
from 9% by weight to 45% by weight, preferably from 15% by weight to 40%
by weight, more preferably from 20% by weight to 40% by weight. If it is
less than 9% by weight, the sharpness of images to be formed will be poor;
but if it is more than 45% by weight, the melt-extruded film will be
cracked.
The reflective support for use in the present invention may have a
waterproof resin coat layer having a white pigment content of 0% by weight
(or containing no white pigment), by which the total content of the white
pigment in the support may be reduced. Even if the total content of the
white pigment in the support is reduced as above, the sharpness of the
photographic material of the present invention is comparable to that of a
photographic material having a reflective support composed of plural resin
coat layers having large white pigment content in total and the white
pigment is uniformly dispersed in a resin coat layer.
The plural waterproof resin coat layers constituting the reflective support
for use in the present invention each have "a different white pigment
content", which means that the effective ratio of the white pigment
content in the layer having a lower white pigment content to that in the
layer having a higher white pigment content may be more than 1 up to
infinity, preferably from 1.1 up to infinity.
To mix a waterproof resin and a white pigment so as to prepare the white
pigment-containing waterproof resin coat layers for the reflective support
of the present invention, the pigment is kneaded into the resin using a
mixing and kneading device such as a two-roll or three-roll kneader, a
Bumbury's mixer, etc. and using a dispersing agent chosen from among metal
salts of higher fatty acids, esters of higher fatty acids, higher fatty
acid amides, higher fatty acids, etc. and formed into a master batch
comprising pellets. The white pigment content in these pellets is, in
general, approximately from 30% by weight to 75% by weight; and the
dispersing agent is, in general, approximately from 0.5% by weight to 10%
by weight, relative to the white pigment.
The waterproof resin layers preferably contain a bluing agent. As the
bluing agent, usable are generally-known ultramarine, cobalt blue, cobalt
phosphate oxide, quinacridone pigments, etc., and their mixtures. The
grain size of the grains of the bluing agent is not specifically defined.
The grain size of the grains of commercial bluing agents is, in general,
approximately from 0.3 .mu.m to 10 .mu.m, which is employable in the
present invention with no problem. The preferred content of the bluing
agent is from 0.1% by weight to 0.5% by weight in the uppermost layer and
is from 0 to 0.7% by weight in the lower layer(s) relative to the
waterproof resin.
The bluing agent is kneaded into a waterproof resin, using a mixing and
kneading device such as a two-roll or three-roll kneader, a Bumbury's
mixer, etc. and shaped into pellets to be a master batch. The content of
the bluing agent in the pellets may be from 1% by weight to 30% by weight.
Preparing the pellets containing the bluing agent, a white pigment may be
kneaded thereinto along with the agent. If desired, a dispersing agent
chosen from among low molecular waterproof resins, metal salts of higher
fatty acids, esters of higher fatty acids, higher fatty acid amides,
higher fatty acids, etc. may be used so as to promote the dispersion of
the bluing agent.
The waterproof resin layers may contain an antioxidant. The content of the
antioxidant is suitably from 50 to 1000 ppm, relative to the waterproof
resin.
The thus-formed master batch containing a white pigment and/or a bluing
agent is suitably diluted with a waterproof resin before use.
To coat the plural waterproof resin coat layers on a base to prepare the
reflective support for use in the present invention, employable is any of
a successive lamination method where the above-mentioned pellets
containing a white pigment and/or a bluing agent are melted under heat,
then optionally diluted with a waterproof resin and laminated successively
on a running base, such as paper or a synthetic paper, or a co-extruding
lamination method where the melts are simultaneously laminated on a
running base through a feed-block-type, multi-manifold-type or
multi-slot-type multi-layer extrusion die. The multi-layer extrusion die
is generally a T-die, a coat hunger die, etc. and is not specifically
defined. The temperature of the melt of the waterproof resin to be
extruded is generally from 280.degree. C. to 340.degree. C., especially
preferably from 310.degree. C. to 330.degree. C., at the outlet of the
die. Before coating the base with the resins, the base is preferably
activated by corona discharging, flame treatment, glow discharging, etc.
The total thickness of the plural white pigment-containing, waterproof
resin coat layers to be formed on the base of the reflective support for
use in the present invention is preferably from 5 to 100 .mu.m, more
preferably from 5 to 80 .mu.m, especially preferably from 10 to 50 .mu.m.
If it is more than 100 .mu.m, the properties of the layers will be
problematic in that the layers are cracked due to the brittleness of the
resin. If, however, it is less than 5 .mu.m, the water-proofness which is
the intrinsic object of the coating will be lost and, in addition, it is
impossible to satisfy both the whiteness and the surface smoothness at the
same time, and the layers will be unfavorably too soft in view of their
physical properties.
The thickness of each of the plural waterproof resin coat layers is
preferably from 0.5 .mu.m to 50 .mu.m. For instance, when the support has
two waterproof resin coat layers, it is preferred that each layer has from
0.5 .mu.m to 50 .mu.m while the total thickness of the two layers falls
within the above-mentioned range.
When the support has three waterproof resin coat layers, it is preferred
that the thickness of the uppermost layer is from 0.5 .mu.m to 10 .mu.m,
that of the interlayer is from 5 mm to 50 .mu.m, and that of the lowermost
layer (nearest to the base) is from 0.5 .mu.m to 30 .mu.m. If the
thickness of the uppermost layer and that of the lowermost layer each are
less than 0.5 .mu.m, die lip streaks will be formed on the coated surface
due to the action of the highly-densified white pigment in the interlayer.
On the other hand, however, if the thickness of the uppermost layer and
the lowermost layer, especially that of the uppermost layer is more than
10 .mu.m, the sharpness of the photographic material will be lowered.
The thickness of the resin or resin composition layer to be coated on the
surface of the base not coated with the emulsion layers is preferably from
5 to 100 .mu.m, more preferably from 10 to 50 .mu.m. If it is more than
the range, the properties of the layer will be problematic in that the
layer is cracked due to the brittleness of the resin. If, however, it is
less than the range, the water-proofness which is the intrinsic object of
the coating will be lost and, in addition, the layer will be unfavorably
too soft in view of its physical properties.
The surface of the uppermost waterproof resin coat layer on which the
emulsion layers are provided is made glossy, or is made fine in such a way
as disclosed in JP-A 55-26507, or is shaped to be a matt or silky surface,
while the back surface thereof is shaped to be non-glossy. After
thus-shaped, the surface of the support may be activated by corona
discharging, flame treatment, etc. In addition, after the activation, the
support may be coated with subbing layer(s) in such a way as disclosed in
JP-A 61-84643.
The base of the reflective support for use in the present invention may be
any of a natural pulp paper made of natural pulp as the essential raw
material, a mixed paper composed of natural pulp and synthetic fibers, a
synthetic fiber paper consisting essentially of synthetic fibers, and a
so-called synthetic paper made of synthetic resin films such as
polystyrene, polypropylene, etc. by papermaking. As a waterproof
resin-coated paper base for the support of photographic printing papers, a
natural pulp paper (hereinafter referred to as a base paper) is especially
advantageously used. To the base paper, various chemicals may be added.
Such chemicals include, for example, a filler such as clay, talc, calcium
carbonate, fine grains of urea resins, etc.; a sizing agent such as rosin,
alkylketene dimers, higher fatty acids, epoxydated higher fatty acid
amides, paraffin wax, alkenylsuccinic acids, etc.; a paper reinforcing
agent such as starch, polyamide-polyamine epichlorohydrins,
polyacrylamides, etc.; and a fixing agent such as alumina sulfate,
cationic polymers, etc. In addition, dyes, fluorescent dyes, a slime
controlling agent, a defoaming agent, etc. may optionally be added to the
base paper. Further, softening agents which will be mentioned below may
also be added thereto, if desired.
Softening agents which may be added to the base paper are described in, for
example, New Handbook for Paper Processing (edited by Shiyaku Times Co.,
1980), pp. 554 to 555. Such compounds have hydrophobic group(s) with 10 or
more carbon atoms along with amine salt(s) or quaternary ammonium salt(s)
capable of self-fixing with cellulose. In particular, those having a
molecular weight of 200 or more are preferred. As concrete examples of
usable softening agents, mentioned are reaction products of maleic
anhydride copolymers and polyalkylenepolyamines, reaction products of
higher fatty acids and polyalkylene-polyamines, reaction products of
urethane alcohols and alkylating agents, quaternay ammonium salts of
higher fatty acids, etc. Of these, especially preferred are reaction
products of maleic anhydride copolymers and polyalkylene-polyamines, and
reaction products of urethane alcohols and alkylating agents.
The surface of the pulp paper may be sized with a film forming polymer such
as gelatin, starch, carboxymethyl cellulose, polyacrylamide, polyvinyl
alcohol, modified products of polyvinyl alcohol, etc. As examples of
modified products of polyvinyl alcohol usable for the purpose, mentioned
are carboxyl-modified products, silanol-modified products, copolymers with
acrylamides, etc. The amount of the film forming polymer to be coated on
the surface of the pulp paper so as to size it with the polymer may be
from 0.1 g/m.sup.2 to 5.0 g/m.sup.2, preferably from 0.5 g/m.sup.2 to 2.0
g/m.sup.2. If desired, the film forming polymer may contain an antistatic
agent, a brightening agent, pigments, a defoaming agent, etc.
The base for the support of the present invention may be produced by making
the above-mentioned pulp or pulp slurry comprising pulp and a filling
agent, a sizing agent, a paper reinforcing agent, a fixing agent, etc.
optionally added thereto into paper, using a papermaking machine such as a
Fourdrinier papermaking machine or the like, and then drying and winding
up the thus-made paper. Before or after the drying step, the paper is
treated with the above-mentioned sizing agent. It is preferred that the
paper is calendered between the drying step and the winding-up step. If
the surface-sizing treatment is effected after drying, the calendering
treatment may be effected either before or after the surface-sizing
treatment. It is preferred that the calendering treatment is effected in
the final finishing step after all the necessary treatments. To conduct
the calendering treatment, used are known metal rolls and elastic rolls
which are used in general papermaking.
The thickness of the base of the support for use in the present invention
is not specifically defined, but the weight thereof is desirably from 50
g/m.sup.2 to 250 g/m.sup.2 and the thickness thereof is desirably from 50
.mu.m to 250 .mu.m.
The support for use in the present invention may be coated with various
backing layers so as to prevent it from being electrically charged and
from being curled. Such backing layers may contain an inorganic antistatic
agent, an organic antistatic agent, a hydrophilic binder, a latex, a
hardening agent, pigments, surfactants, etc., as combined suitably, such
as those described or illustrated in JP-B 52-18020, 57-9059, 57-53940,
58-56859, and JP-A 59-214849, 58-184144. (The term "JP-B" as used herein
means an "examined Japanese patent publication".)
Cyan couplers of formula (Ia) for use in the present invention are
concretely represented by the following general formulae (IIa) to (VIIIa):
##STR3##
In these formulae (IIa) to (VIIIa), R.sub.1, R.sub.2, R.sub.3, R.sub.4 and
X have the same meanings as those in formula (Ia).
Of these cyan couplers, those of formulae (IIa), (IIIa) and (IVa) are
preferred, and those of formula (IIIa) are especially preferred.
Next, couplers of formula (Ib) for use in the present invention will be
described below.
In formula (Ib), R.sub.4 and X have the same meanings as those in formula
(Ia).
In formula (Ib), R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9 each
represent a hydrogen atom or a substituent, having the same meaning as
R.sub.4 in formula (Ia).
Z represents a non-metallic atomic group necessary for forming a ring. The
non-metallic atomic group of Z may optionally be substituted by
substituent(s). The ring to be formed by Z may be either an aromatic ring
or a hetero ring. When it is an aromatic ring or an aromatic hetero ring,
the formula does not have R.sub.7, R.sub.8 and R.sub.9. The ring to be
formed by Z is preferably a 5-membered to 7-membered ring, for example
including substituted or unsubstituted alicyclic hydrocarbons such as
cyclohexane ring, cyclopentane ring, etc., and substituted or
unsubstituted aromatic rings such as typically benzene ring. As the
substituents for these rings, those mentioned for R.sub.4 hereinabove are
referred to. R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9 and the
substituents on Z may be bonded to each other to form ring(s), preferably
3-membered to 7-membered ring(s). As one example of such condensed rings,
mentioned is an adamantyl group.
In the cyan couplers of the present invention, R.sub.1, R.sub.2 and R.sub.3
each represent an electron-attracting group having a Hammett's substituent
constant .sigma.p of 0.20 or more. The sum of the .sigma.p values of
R.sub.1 and R.sub.2 is 0.65 or more, preferably 0.70 or more. The
uppermost limit of the sum is about 1.8.
R.sub.1, R.sub.2 and R.sub.3 each represent an electron-attracting group
having a Hammett's substituent constant .sigma.p of 0.20 or more,
preferably 0.35 or more, more preferably 0.45 or more. The uppermost limit
of the .sigma.p value of the electron-attracting group is preferably 1.0,
more preferably 0.75. The Hammett's rule is an empirical rule that was
proposed by L. P. Hammett in 1935 so as to quantitatively deal with the
influence of substituents on the reaction or equilibrium of benzene
derivatives and its reasonability has been widely admitted in this
technical field in these days. The substituent constants to be obtained on
the basis of the Hammett's rule are .sigma.p and .sigma.m values, which
are described in various ordinary literatures. For example, the details
thereof are described in J. A. Dean, Lange's Handbook of Chemistry, 12th
Ed., 1979 (McGraw-Hill) in Kaqaku no Ryoiki (The Domain of Chemistry),
Extra Edition, No. 122, pp. 96 to 103, 1979, published by Nankodo. In the
present invention, R.sub.1, R.sub.2 and R.sub.3 are defined by their
Hammett's substituent constant .sigma.p values. However, these are not
limited to only substituents whose .sigma.p values are known in published
literatures but, as a matter of course, they include all substituents
having .sigma.p values falling within the defined range when measured on
the basis of the Hammett's rule even though their .sigma.p values are not
described in published literatures.
As specific examples of the electron-attracting group having a .sigma.p
value of 0.20 or more, for R.sub.1, R.sub.2 and R.sub.3, mentioned are an
acyl group, an acyloxy group, carbamoyl group, an alkoxycarbonyl group, an
aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono
group, a diarylphosphono group, a diarylphosphinyl group, an alkylsulfinyl
group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl
group, a sulfonyloxy group, an acylthio group, a sulfamoyl group, a
thiocyanato group, a thiocarbonyl group, a halogenoalkyl group, a
halogenoalkoxy group, halogenoaryloxy group, a halogenalkylamino group, ha
logenoalkyl thio group, an aryl group substituted by electron-attracting
group(s) having an .sigma.p value of 0.20 or more, a heterocyclic group, a
halogen atom, an azo group and a selenocyanato group. These groups may
optionally be substituted by substituent(s) such as those for R.sub.4 to
be mentioned hereunder.
More precisely, R.sub.1, R.sub.2 and R.sub.3 each represent an
electron-attracting group having an .sigma.p value of 0.20 or more, such
as an acyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl,
4-dodecyloxybenzoyl), an acyloxy group (e.g., acetoxy), a carbamoyl group
(e.g., carbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl,
N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl,
N-(4-n-pentadecanamido) phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl,
N-{3-(2,4-di-t-amylphenoxy)propyl}carbamoyl), an alkoxycarbonyl group
(e.g., methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl,
tert-butyloxycarbonyl, iso-butyloxycarbonyl, butyloxycarbonyl,
dodecyloxycarbonyl, octadecyloxycarbonyl, diethylcarbamoylethoxycarbonyl,
perfluorohexylethoxycarbonyl, 2-decyl-hexyloxycarbonylmethoxycarbonyl), an
aryloxycarbonyl group (e.g., phenoxycarbonyl, 2,5-amylphenoxycarbonyl), a
cyano group, a nitro group, a dialkylphosphono group (e.g.,
dimethylphosphono), a diarylphosphono group (e.g., diphenylphosphono), a
dialkoxyphosphoryl group (e.g., dimethoxyphosphoryl), a diarylphosphinyl
group (e.g., diphenylphosphinyl), an alkylsulfinyl group (e.g.,
3-phenoxypropylsulfinyl), an arylsulfinyl group (e.g.,
3-pentadecylphenylsulfinyl), an alkylsulfonyl group (e.g.,
methanesulfonyl, octanesulfonyl), an arylsulfonyl group (e.g.,
benzenesulfonyl, toluenesulfonyl), a sulfonyloxy group (e.g.,
methanesulfonyloxy, toluenesulfonyloxy), an acylthio group (e.g.,
acetylthio, benzoylthio), a sulfamoyl group (e.g., N-ethylsulfamoyl,
N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl,
N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl), a thiocyanato group, a
thiocarbonyl group (e.g., methylthiocarbonyl, phenylthiocarbonyl), a
halogenoalkyl group (e.g., trifluoromethyl, heptafluoropropyl), a
halogenoalkoxy group (e.g., trifluoromethyloxy), a halogenoaryloxy group
(e.g., pentafluorophenyloxy), a halogenoalkylamino group (e.g. ,
N,N-di(trifluoromethyl)amino), a halogenoalkylthio group (e.g.,
difluoromethylthio, 1,1,2,2-tetrafluoroethylthio), an aryl group
substituted by other electron-attracting group(s) having a .sigma.p value
of 0.20 or more (e.g., 2,4-dinitrophenyl, 2,4,6-trichlorophenyl,
pentachlorophenyl), a heterocyclic group (e.g., 2-benzoxazolyl,
2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, pyrazolyl,
5-chloro-1-tetrazolyl, 1-pyrrolyl), a halogen atom (e.g., chlorine,
bromine), an azo group (e.g., phenylazo) or a selenocyanato group.
Typical electron-attracting groups will be mentioned along with their
.sigma.p values as parenthesized: Cyano group (0.66), nitro group (0.78),
trifluoromethyl group (0.54), acetyl group (0.50),
trifluoromethanesulfonyl group (0.92), methanesulfonyl group (0.72),
benzenesulfonyl group (0.70), methanesulfinyl group (0.49), carbamoyl
group (0.36), methoxycarbonyl group (0.45), pyrazolyl group (0.37),
methanesulfonyloxy group (0.36), dimethoxyphosphoryl group (0.60),
sulfamoyl group (0.57).
Preferably, R.sub.1, R.sub.2 and R.sub.3 each are an acyl group, an acyloxy
group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl
group, a cyano group, a nitro group, an alkylsulfinyl group, an
arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a
sulfamoyl group, a halogenoalkyl group, a halogenoalkyloxy group, a
halogenoalkylthio group, a halogenoaryloxy group, a halogenoaryl group, an
aryl group substituted by two or more nitro groups, or a heterocyclic
group. More preferably, they each are an acyl group, an alkoxycarbonyl
group, an aryloxycarbonyl group, a nitro group, a cyano group, an
arylsulfonyl group, a carbamoyl group or a halogenoalkyl group; especially
preferably they each are a cyano group, an alkoxycarbonyl group, an
aryloxycarbonyl group or a halogenoalkyl group.
Further preferably, they each are a cyano group, a fluoroalkyl group, a
sulfamoyl group or an alkoxycarbonyl group. Preferred combinations of
R.sub.1 and R.sub.2 are such that R.sub.1 is a cyano group and R.sub.2 is
a fluoroalkyl group or an alkoxycarbonyl group. Especially preferably,
R.sub.1 is a cyano group and R.sub.2 is an alkoxycarbonyl group. In such
combinations, R.sub.2 is preferably an alkoxycarbonyl group having a
branched alkyl chain or an alkoxycarbonyl group having a cyclic alkyl
chain, especially preferably an alkoxycarbonyl group having a cyclic alkyl
chain.
R.sub.4 represents a hydrogen atom or a substituent (including atoms). As
examples of the substituent for R.sub.4, mentioned are a halogen atom, an
aliphatic group, an aryl group, a heterocyclic group, an alkoxy group, an
aryloxy group, a heterocyclic-oxy group, an alkyl-, aryl- or
heterocyclic-thio group, an acyloxy group, a carbamoyloxy group, a
silyloxy group, a sulfonyloxy group, an acylamino group, an alkylamino
group, an arylamino group, an ureido group, a sulfamoylamino group, an
alkenyloxy group, a formyl group, an alkyl-, an aryl- or heterocyclic-acyl
group, an alkyl-, aryl- or heterocyclic-sulfonyl group, an alkyl-, aryl-
or heterocyclic-sulfinyl group, an alkyl-, aryl- or
heterocyclic-oxycarbonyl group, an alkyl-, aryl- or
heterocyclic-oxycarbonylamino group, a sulfonamido group, a carbamoyl
group, a sulfamoyl group, a phosphonyl group, a sulfamido group, an imido
group, a hydroxyl group, a cyano group, a carboxyl group, a nitro group, a
sulfo group, and an unsubstituted amino group. The alkyl, aryl and
heterocyclic moieties in these groups may optionally be substituted by
substituent(s) such as those mentioned for R.sub.4 hereinabove.
More precisely, R.sub.4 represents a hydrogen atom, a halogen atom (e.g.,
chlorine, bromine), an aliphatic hydrocarbon residue, such as a linear or
branched alkyl, aralkyl, alkenyl or alkynyl group having from 1 to 36
carbon atoms, or an alicyclic hydrocarbon residue such as a cycloalkyl or
cycloalkenyl group (precisely, methyl, ethyl, propyl, isopropyl, t-butyl,
tridecyl, 2-methanesulfonylethyl, 3-( 3-pentadecylphenoxy)propyl,
3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamido}phenyl}propyl,
2-ethoxytridecyl, trifluoromethyl, cyclopentyl,
3-(2,4-di-t-amylphenoxy)propyl), or an aryl group (preferably having from
6 to 36 carbon atoms, such as phenyl, naphthyl, 4-hexadecyloxyphenyl,
4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl,
3-(2,4-tert-amylphenoxyacetamido)phenyl), a heterocyclic group (e.g.,
3-pyridyl, 2-furyl, 2-thienyl, 2-pyridyl, 2-pyrimidinyl,
2-benzothiazolyl), an alkoxy group (e.g., methoxy, ethoxy,
2-methoxyethoxy, 2-dodecyloxyethoxy, 2-methanesulfonylethoxy), an aryloxy
group (e.g., phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy,
2,4-di-tertamylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy, 3-nitrophenoxy,
3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), an alkyl-, aryl-
or heterocyclic-thio group (e.g. , methylthio, ethylthio, octylthio,
tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio,
3-(4-tert-butylphenoxy)propylthio, phenylthio,
2-butoxy-5-tert-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenyl
thio, 4-tetradecanamidophenylthio, 2-benzothiaozlylthio,
2,4-di-phenoxy-1,3,4-triazol-6-thio, 2-pyridylthio), an acyloxy group
(e.g., acetoxy, hexadecanoyloxy), a carbamoyloxy group (e.g.,
N-ethylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (e.g. ,
trimethylsilyloxy, dibutylmethylsilyloxy), a sulfonyloxy group (e.g.,
dodecylsulfonyloxy), an acylamino group (e.g., acetamido, benzamido,
tetradecanamido, 2-(2,4-di-tert-amylphenoxy)acetamido,
2-[4-(4-hydroxyphenylsulfonyl)phenoxy]decanamido, isopentadecanamido,
2-(2,4-di-t-amylphenoxy)butanamido,
4-(3-t-butyl-4-hydroxyphenoxy)butanamido), an alkylamino group (e.g.,
methylamino, butylamino, dodecylamino, dimethylamino, diethylamino,
methylbutylamino), an arylamino group (e.g., phenylamino, 2-chloroanilino,
2-chloro-5-tetradecanamidoanilino, N-acetylanilino,
2-chloro-5-[.alpha.-2-tert-butyl-4-hydroxyphenoxy)dodecanamido]anilino,
2-chloro-5-dodecyloxycarbonylanilino), an ureido group (e.g.,
methylureido, phenylureido, N,N-dibutylureido, dimethylureido), a
sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino,
N-methyl-N-decylsulfamoylamino), an alkenyloxy group (e.g.,
2-propenyloxy), a formyl group, an alkyl-, aryl- or heterocyclic-acyl
group (e.g., acetyl, benzoyl, 2,4-di-tert-amylphenylacetyl,
3-phenylpropanoyl, 4dodecyloxybenzoyl), an alkyl-, aryl- or
heterocyclicsulfonyl group (e.g., methanesulfonyl, octanesulfonyl,
benzenesulfonyl, toluenesulfonyl), an alkyl-, aryl- or
heterocyclic-sulfinyl group (e.g., octanesulfinyl, dodecanesulfinyl,
phenylsulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), an
alkyl-, aryl- or heterocyclic-oxycarbonyl group (e.g., methoxycarbonyl,
butoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl,
phenyloxycarbonyl, 2-pentadecyloxycarbonyl), an alkyl-, aryl- or
heterocyclic-oxycarbonylamino group (e.g., methoxycarbonylamino,
tetradecyloxycarbonylamino, phenoxycarbonylamino,
2,4-di-tert-butylphenoxycarbonylamino), a sulfonamido group (e.g.,
methanesulfonamido, hexadecanesulfonamido, benzenesulfonamido,
p-toluenesulfonamido, octadecanesulfonamido,
2-methoxy-5-tert-butylbenzenesulfonamido), a carbamoyl group (e.g.,
N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxy-ethyl)carbamoyl,
N-methyl-N-dodecylcarbamoyl,
N-[3-(2,4-di-tert-amylphenoxy)propyl]carbamoyl), a sulfamoyl group (e.g.,
N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl,
N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl), a phosphonyl group
(e.g., phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), a
sulfamido group (e.g., dipropylsulfamoylamino), an imido group (e.g.,
N-succinimido, hydantoinyl, N-phthalimido, 3-octadecenylsuccinimido), a
hydroxyl group, a cyano group, a carboxyl group, a nitro group, a sulfo
group, or an unsubstituted amino group.
Preferably, R.sub.4 is an alkyl group, an aryl group, a heterocyclic group,
a cyano group, a nitro group, an acylamino group, an arylamino group, an
ureido group, a sulfamoylamino group, an alkylthio group, an arylthio
group, a heterocyclic-thio group, an alkoxycarbonylamino group, an
aryloxycarbonylamino group, a sulfonamido group, a carbamoyl group, a
sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, an
aryloxycarbonyl group, a heterocyclic-oxy group, an acyloxy group, a
carbamoyloxy group, an imido group, a sulfinyl group, a phosphonyl group,
an acyl group, or an azolyl group.
More preferably, R.sub.4 is an alkyl group or an aryl group. Further
preferably, it is an alkyl or aryl group having at least one substituent
chosen from among an alkoxy group, a sulfonyl group, a sulfamoyl group, a
carbamoyl group, an acylamido group and a sulfonamido group. Especially
preferably, it is an aryl group having an ortho-positioned alkoxy or
alkylamino group. In the alkoxy moiety in this group, the structure
bonding to the oxygen atom may comprise a linear alkyl, branched alkyl,
cyclic alkyl or substituted alkyl group. As specific examples of the
structure, mentioned are methyl, ethyl, isopropyl, hexyl, 2-ethyl-hexyl,
octyl, benzyl and 2,6-dimethylcyclohexyl groups, which, however, are not
limitative. The alkylamino group may be either a monoalkylamino group or a
dialkylamino group. The alkyl moiety in the group may be either linear or
branched or may have substituent(s). As specific examples of the group,
mentioned are monomethylamino, dimethylamino, diethylamino and
diisopropylamino groups, which, however, are not limitative. The aryl
group having an ortho-positioned alkoxy or alkylamino group may have other
substituent(s) than the ortho-substituent. As examples of such additional
substituents, mentioned are an acylamino group, a sulfonylamino group and
a halogen atom.
In formula (Ia), X represents a hydrogen atom or a group capable of
splitting off from the compound when the coupler reacts with an oxidation
product of an aromatic primary amine color developing agent (hereinafter
referred to as a "split-off group"). As examples of the split-off group,
mentioned are a halogen atom, an aromatic azo group, or an alkyl, aryl or
heterocyclic group bonded to the coupling position of the formula via a
linking group containing, as a split-off atom, an oxygen, nitrogen, sulfur
or carbon atom (including a nitrogen-containing heterocyclic group bonded
to the coupling position via the nitrogen atom of the hetero ring in the
group). The linking group includes, for example, --O--, --NH--, --S--,
--SO--, --SO.sub.2 --, --CO--, --CON.dbd., --SO.sub.2 O--, --OCOO--,
--SO.sub.2 NH--, --OCO--, and combinations of two or more of these groups.
Precisely, mentioned are a halogen atom, an alkoxy group, an aryloxy
group, an acyloxy group, an alkyl- or aryl-sulfonyloxy group, an acylamino
group, an alkyl- or aryl-sulfonamido group, an alkoxycarbonyloxy group, an
aryloxycarbonyloxy group, an alkyl-, aryl- or heterocyclic-thio group, a
carbamoylamino group, an arylsulfinyl group, an arylsulfonyl group, a
5-membered or 6-membered nitrogen-containing heterocyclic group, an imido
group, and an arylazo group. The alkyl, aryl and heterocyclic moieties in
these split-off groups may optionally be substituted by substituent(s)
such as those mentioned for R.sub.4 hereinabove. If these moieties are
substituted by plural substituents, the plural substituents may be the
same or different and may further be substituted by substituent(s) such as
those mentioned for R.sub.4 hereinabove.
More precisely, the split-off group for X is a halogen atom (e.g.,
fluorine, chlorine, bromine), an alkoxy group (e.g. , ethoxy, dodecyloxy,
methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy,
ethoxycarbonylmethoxy), an aryloxy group (e.g., 4-methylphenoxy,
4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy,
3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), an
acyloxy group (e.g., acetoxy, tetradecanoyloxy, benzoyloxy), an alkyl- or
aryl-sulfonyloxy group (e.g., methanesulfonyloxy, toluenesulfonyloxy), an
acylamino group (e.g., dichloroacetylamino, heptafluorobutyrylamino), an
alkyl- or aryl-sulfonamido group (e.g., methanesulfonamino,
trifluoromethanesulfonamino, p-toluenesulfonylamino), an alkoxycarbonyloxy
group (e.g., ethoxycarbonyloxy, benzyloxycarbonyloxy), an
aryloxycarbonyloxy group (e.g. , phenoxycarbonyloxy), an alkyl-, aryl- or
heterocyclic-thio group (e.g., ethylthio, 2-carboxyethylthio, dodecylthio,
1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio,
tetrazolylthio), an arylsulfonyl group (e.g.,
2-butoxy-5-tert-octylphenylsulfonyl), an arylsulfinyl group (e.g.,
2-butoxy-5-tert-octylphenylsulfinyl), a carbamoylamino group (e.g.,
N-methylcarbamoylamino, N-phenylcarbamoylamino), a 5-membered or
6-membered nitrogen-containing heterocyclic group (e.g., imidazolyl,
pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), an imido
group (e.g., succinimido, hydantoinyl), or an arylazo group (e.g.,
phenylazo, 4-methoxyphenylazo). As a matter of course, these split-off
groups may optionally be substituted by substituent(s) such as those
mentioned for R.sub.4 hereinabove. As examples of the split-off group
bonded thereto via a carbon atom, mentioned are residues derived from
bis-type couplers to be obtained by condensation of 4-equivalent couplers
with aldehydes or ketones. The split-off group as referred to herein may
contain a photographically-useful group such as a residue of a development
inhibitor or a development accelerator.
Preferably, X is a halogen atom, an alkoxy group, an aryloxy group, an
alkyl- or aryl-thio group, an arylsulfonyl group, an arylsulfinyl group,
or a 5-membered or 6-membered nitrogen-containing heterocyclic group
bonded to the coupling position of the compound via a nitrogen atom. More
preferably, X is an arylthio group.
Cyan couplers of formula (Ia) may be dimers or higher polymers, in which
R.sub.1, R.sub.2, R.sub.3, R.sub.4 or X contains a residue of the cyan
coupler of formula (Ia); or they may be homopolymers or copolymers in
which R.sub.1, R.sub.2, R.sub.3, R.sub.4 or X contains polymer chain(s).
As typical examples of homopolymers or copolymers containing polymer
chain(s), mentioned are homopolymers or copolymers formed of
addition-polymerizable ethylenic unsaturated compounds having a residue of
the cyan coupler of formula (Ia). Such homopolymers or copolymers may
contain one or more cyan-coloring repeating units containing a residue of
the cyan coupler of formula (Ia). The copolymers may contain one or more
non-coloring ethylenic comohomers that do not couple with an oxidation
product of an aromatic primary amine developing agent, such as acrylates,
methacrylates, maleates, etc.
Specific examples of the cyan couplers of the present invention are
mentioned below, which, however, are not intended to restrict the scope of
the present invention.
-
##STR4##
(1)
##STR5##
(2)
##STR6##
(3)
##STR7##
(4)
##STR8##
(5)
##STR9##
(6)
##STR10##
(7)
No. R.sub.1 R.sub.2 R.sub.4 X
##STR11##
8 CO.sub.2
CH.sub.3 CN
##STR12##
H
9 CN
##STR13##
##STR14##
H
10 CN
##STR15##
##STR16##
H
11 CN
##STR17##
##STR18##
Cl
12 CN
##STR19##
##STR20##
H
13 CN
##STR21##
##STR22##
Cl
14 CN
##STR23##
##STR24##
Cl
15 CN
##STR25##
##STR26##
##STR27##
16 CN CO.sub.2 CH.sub.2 CH.sub.2 (CF.sub.2).sub.6
F
##STR28##
##STR29##
17 CN
##STR30##
##STR31##
##STR32##
18 CN
##STR33##
##STR34##
##STR35##
19 CN
##STR36##
##STR37##
##STR38##
20 CN CO.sub.2 CH.sub.2 (CF.sub.2).sub.4
H
##STR39##
##STR40##
21 CN
##STR41##
##STR42##
Cl
22
##STR43##
CN
##STR44##
##STR45##
23 CO.sub.2 CH.sub.2 C.sub.6
F.sub.13 CN
##STR46##
Cl
24
##STR47##
##STR48##
CH.sub.3 OCOCH.sub.3
25 CN CO.sub.2 CH.sub.2 CO.sub.2
CH.sub.3
##STR49##
##STR50##
26 CN
##STR51##
##STR52##
##STR53##
27 CN
##STR54##
##STR55##
Cl
28
##STR56##
CF.sub.3
##STR57##
F
29 CN
##STR58##
##STR59##
##STR60##
30
##STR61##
##STR62##
##STR63##
##STR64##
31 CN
##STR65##
##STR66##
##STR67##
32 CN
##STR68##
##STR69##
H
33 CN
##STR70##
##STR71##
OSO.sub.2
CH.sub.3
34 CN COOC.sub.14 H.sub.29
(sec)
##STR72##
Cl
35 CN
##STR73##
##STR74##
Cl
36 CN
##STR75##
##STR76##
Cl
37 CN
##STR77##
##STR78##
Cl
38 CN
##STR79##
##STR80##
Cl
39 CN
##STR81##
##STR82##
Cl
40 CN
##STR83##
##STR84##
Cl
41 CN
##STR85##
##STR86##
##STR87##
42 CN
##STR88##
##STR89##
Cl
##STR90##
43 CO.sub.2 C.sub.2
H.sub.5 CN
##STR91##
Cl
44 CN
##STR92##
##STR93##
H
45 CN CO.sub.2 CH.sub.2 CH.sub.2 (CF.sub.2).sub.6
F
##STR94##
##STR95##
46 CN
##STR96##
##STR97##
##STR98##
47 CN
##STR99##
##STR100##
##STR101##
48 CN
##STR102##
##STR103##
H
49 CN
##STR104##
##STR105##
Cl
50 CN
##STR106##
##STR107##
OSO.sub.2
CH.sub.3
##STR108##
(51)
##STR109##
(52)
##STR110##
(53)
##STR111##
(54)
##STR112##
(55)
Compounds of the present invention and intermediates for producing them may
be produced by known methods. For instance, they may be produced by the
methods described in J. Am. Chem. Soc. No. 80, 5332 (1958); J. Am. Chem.
Soc., No. 81, 2452 (1959); J. Am. Chem. Soc., No. 112, 2465 (1990); Org.
Synth., I, 270 (1941); J. Chem. Soc., 5149 (1962); Heterocycles, No. 27,
2301 (1988); Rec. Trav. Chim., 80, 1075 (1961); or in the literatures
referred to in these publications; or by methods similar to the described
methods.
One production example will be mentioned below, which demonstrates the
production of Cyan Coupler No. 9 illustrated hereinabove.
Production Example 1: Production of Compound No. 9:
Compound No. 9 was produced according to the reaction scheme mentioned
below.
##STR113##
Precisely, 2-methoxybenzoyl chloride (2a) (83.2 g, 0.4 mol) was added to a
dimethylacetamide (300 ml) solution containing
2-amino-4-cyano-3-ethoxycarbonylpyrrole (Ia) (66.0 g, 0.4 mol) at room
temperature, and stirred for 30 minutes. Water was added to the reaction
mixture, which was then extracted two times each with ethyl acetate. The
organic layers were combined, washed with water and a saturated aqueous
salt solution, and dried with anhydrous sodium sulfate. The solvent was
removed by distillation under reduced pressure, and the residue was
recrystallized from acetonitrile (300 ml) to obtain Compound (3a) (113 g,
84%).
Powder of potassium hydroxide (252 g, 4.5 mol) was added to a
dimethylformamide (200 ml) solution containing Compound (3a) (101.1 g, 0.3
mol) at room temperature and well stirred. While cooling with water,
hydroxylamine-o-sulfonic acid (237 g, 2.1 mol) was added thereto, little
by little, in such a way that the reaction temperature was controlled so
as not to rise too rapidly. After the addition, this was stirred for 30
minutes. An aqueous 0.1 N-hydrochloric acid solution was dropwise added
thereto, by which this was neutralized while checking it using pH test
papers. This was then extracted three times each with ethyl acetate. The
organic layers were washed with water and a saturated aqueous salt
solution and dried with anhydrous sodium sulfate. The solvent was removed
by distillation under reduced pressure, and the residue was purified by
column chromatography (using, as the developing solvent, hexane/ethyl
acetate=2/1) to obtain Compound (4a) (9.50 g, 9%).
Carbon tetrachloride (9 cc) was added to an acetonitrile (30 ml) solution
containing Compound (4a) (7.04 g, 20 mmol) at room temperature, and then
triphenylphosphine (5.76 g, 22 mmol) was added thereto and heated under
reflux for 8 hours. After cooled, water was added thereto. This was then
extracted three times each with ethyl acetate. The organic layers were
washed with water and a saturated aqueous salt solution, and dried with
anhydrous sodium sulfate. The solvent was removed by distillation under
reduced pressure, and the residue was purified by silica gel column
chromatography (using, as the developing solvent, hexane/ethyl
acetate=4/1) to obtain Compound (5a) (1.13 g, 17%).
The thus-obtained Compound (5a) (1.8 g) and Compound (6a) (12.4 g) were
dissolved in sulforane (2.0 ml), and titanium isopropoxide (1.5 g) was
added thereto. These were reacted for 1.5 hours, while the reaction
temperature was maintained at 200.degree. C. After thus reacted, ethyl
acetate was added thereto. Then, this was washed with water. The ethyl
acetate layer was dried and subjected to distillation. The resulting
residue was purified by column chromatography to obtain 1.6 g of the
intended Coupler No. 9. This had a melting point of 210.degree. to
212.degree. C.
To apply the cyan coupler of formula (Ia) of the present invention to a
silver halide color photographic material, the material may have at least
one layer containing the coupler on the support. The layer containing the
coupler of the present invention may be a hydrophilic colloid layer to be
on the support. In general, an ordinary color photographic material has at
least one blue-sensitive silver halide emulsion layer, at least one
green-sensitive silver halide emulsion layer and at least one
red-sensitive silver halide emulsion layer on the support in this order.
However, such constitution is not limitative. The photographic material of
the present invention may have any other constitutions different from
this. In view of the rapid processability of the photographic material, it
is often preferred that the material has, as the uppermost layer, a
light-sensitive layer containing silver halide grains having the largest
mean grain size. In view of its storability in light, it is often
preferred that the material has, as the lowermost layer, a
magenta-coloring light-sensitive layer.
If desired, the photographic material may have an infrared-sensitive silver
halide emulsion layer in place of at least one of the above-mentioned
light-sensitive emulsion layers. These light-sensitive emulsion layers
each may comprise a silver halide emulsion having a sensitivity to the
respective wavelength ranges and a color coupler of forming a dye having a
complementary color to the light to which the emulsion is sensitive,
whereby color reproduction by subtractive color photography may be
effected. The relationship between the light-sensitive emulsion layer and
the color hue of the dye to be formed from the color coupler in the layer
is not limited to the above-mentioned constitution but may be of any
others.
The coupler of formula (Ia) of the present invention is especially
preferably added to the red-sensitive silver halide emulsion layer.
The amount of the coupler of the present invention to be added to the
photographic material is generally from 1.times.10.sup.-3 mol to 1 mol,
preferably from 2.times.10.sup.-3 mol to 5.times.10.sup.-1 mol, per mol of
the silver halide in the layer to which the coupler is added.
The content of the cyan coupler(s) of the present invention in the
photographic material is preferably such that the color difference between
the cyan color area and the minimum density area in the material is 23 or
more, more preferably 24 or more, when the density of the cyan color image
formed is 0.4.
The color difference between the cyan color area and the minimum density
area as referred to herein may be obtained by coating, on a reflective
support having a smooth surface, a photographic constitutive layer
containing a silver halide emulsion containing a varying amount of a cyan
coupler, exposing the resulting photographic material to light having a
suitable spectral composition, developing it to obtain cyan color patches
having various color densities and a white background patch, and measuring
the spectral absorption of each patch. The spectral absorption of each
patch is effected under the condition (c) defined by JIS Z-8722 (1982)
relating to the geometric conditions for radiation and light reception of
photographic materials, whereupon the tristumulus values X, Y and Z under
a D65 light source are obtained by the method defined by the same JIS
Z-8722 (1982) are obtained from the measured data. From the thus-measured
values, the values of L*, a* and b* of each sample are obtained by the
method defined by JIS Z-8729 (1980), and the intended color difference is
obtained according to the method defined by JIS Z-8730 (1980).
It is preferred that the silver halide color photographic material of the
present invention contains, in its cyan coupler-containing silver halide
emulsion layer, at least one chosen from among oleophilic compounds of the
following general formulae (A), (B) and (C), that chemically bond to an
aromatic primary amine color developing agent under the condition of pH 8
or less to give substantially colorless products, and/or at least one
chosen from among oleophilic compounds of the following general formula
(D) that chemically bond to an oxidation product of an aromatic primary
amine color developing agent under the condition of pH 8 or less to give
substantially colorless products.
##STR114##
These oleophilic compounds of formulae (A), (B), (C) and (D) are effective
for preventing cyan stains.
In formula (A), L.sub.al represents a single bond, --O--, --S--, --CO-- or
--N(R.sub.a2)--; R.sub.a1 and R.sub.a2 may be the same or different and
each represents an aliphatic group, an aromatic group or a heterocyclic
group, and R.sub.a2 may also be a hydrogen atom, an acyl group, a sulfonyl
group, a carbamoyl group or a sulfamoyl group; Z.sub.a1 represents an
oxygen atom or a sulfur atom; Z.sub.a2 represents a hydrogen atom,
--O--R.sub.a3, --S--R.sub.a4, --L.sub.a2 --C(.dbd.Z.sub.z1 '0R.sub.z5, or
a heterocyclic group bonding to the formula via a nitrogen atom; R.sub.a3
and R.sub.a4 may be the same or different and each represents a vinyl
group, an aromatic group or a heterocyclic group, which may optionally be
substituted; L.sub.a2 represents --O-- or --S--; Z.sub.a1 ' has the same
meaning as Z.sub.a1 ; R.sub.a5 represents an aliphatic group, an aromatic
group or a heterocyclic group; and at least two of R.sub.a1, R.sub.a2 and
Z.sub.a2 may be bonded to each other to form a 5-membered to 7-membered
ring.
In formula (B), R.sub.b1 represents an aliphatic group; and Z.sub.b1
represents a halogen atom.
In formula (C), Z.sub.c1 represents a cyano group, an acyl group, a formyl
group, an aliphatic-oxycarbonyl group, an aromatic-oxycarbonyl group, a
carbamoyl group, a sulfamoyl group, or a sulfonyl group; R.sub.c1,
R.sub.c2 and R.sub.c3 may be the same or different and each represents a
hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group
or Z.sub.c1 ; and at least two of R.sub.c1, R.sub.c2, R.sub.c3 and
Z.sub.c1 may be bonded to each other to form a 5-membered to 7-membered
ring.
In formula (D), R.sub.d1 represents an aliphatic group or an aromatic
group; Z.sub.d1 represents a mercapto group or --SO.sub.2 Y; Y represents
a hydrogen atom, an atom or atomic group for forming an inorganic or
organic salt, --NHN.dbd.C(R.sub.d2)R.sub.d3,
--N(R.sub.d4)--N(R.sub.d5)--SO.sub.2 R.sub.d6,
--N(R.sub.d7)--N(R.sub.d8)--COR.sub.d9 or --C(R.sub.d10)
(OR.sub.d11)--COR.sub.d12 ; R.sub.d2 and R.sub.d3 may be the same or
different and each represents a hydrogen atom, an aliphatic group, an
aromatic group or a heterocyclic group, provided that R.sub.d2 and
R.sub.d3 may be bonded to each other to form a 5-membered to 7-membered
ring; R.sub.d4, R.sub.d5, R.sub.d7 and R.sub.d8 may be the same or
different and each represents a hydrogen atom, an aliphatic group, an
aromatic group, a heterocyclic group, an acyl group, an
aliphatic-oxycarbonyl group, a sulfonyl group, an ureido group or an
urethane group, provided that at least one of R.sub.d4 and R.sub.d5 and at
least one of R.sub.d7 and R.sub.d8 are hydrogen atoms; R.sub.d6 and
R.sub.d9 each represent a hydrogen atom, an aliphatic group, an aromatic
group or a heterocyclic group; R.sub.d6 may also be an aliphatic amino
group, an aromatic amino group, an aliphatic-oxy group, an aromatic-oxy
group, an acyl group, an aliphatic-oxycarbonyl group or an
aromatic-oxycarbonyl group; at least two of R.sub.d4, R.sub.d5 and
R.sub.d6 may be bonded to each other to form a 5-membered to 7-membered
ring, and at least two of R.sub.d7, R.sub.d8 and R.sub.d9 may be bonded to
each other to form a 5-membered to 7-membered ring; R.sub.d12 represents a
hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic
group; R.sub.d10 represents a hydrogen atom, an aliphatic group, an
aromatic group, a halogen atom, an acyloxy group or a sulfonyl group; and
R.sub.d11 represents a hydrogen atom or a hydrolyzable group.
Compounds of formulae (A), (B), (C) and (D) for use in the present
invention will be explained in more detail hereunder.
R.sub.a1 and R.sub.a2 are referred to. The aliphatic group includes, for
example, methyl, i-propyl, t-butyl, benzyl, 2-hydroxybenzyl, cyclohexyl,
t-octyl, vinyl, allyl and n-pentadecyl groups. Preferably, it is an
optionally substituted alkyl group having from 1 to 30 carbon atoms. The
aromatic group includes, for example, phenyl and naphthyl groups.
Preferably, it is an optionally substituted phenyl group having from 6 to
36 carbon atoms. The heterocyclic group includes, for example, thienyl,
furyl, chromanyl, morpholinyl, piperazyl and indolyl groups. The acyl
group for R.sub.a2 includes, for example, acetyl, tetradecanoyl and
benzoyl groups. It is preferably an optionally substituted acyl group
having from 2 to 37 carbon atoms. The sulfonyl group includes, for
example, methanesulfonyl and benzenesulfonyl groups. It is preferably an
optionally substituted sulfonyl group having from 1 to 36 carbon atoms.
The carbamoyl group includes, for example, methylcarbamoyl,
diethylcarbamoyl, octylcarbamoyl, phenylcarbamoyl and
N-methyl-N-phenylcarbamoyl groups. Preferably, it is an optionally
substituted carbamoyl group having from 2 to 37 carbon atoms. The
sulfamoyl group includes, for example, methylsulfamoyl, diethylsulfamoyl,
octylsulfamoyl, phenylsulfamoyl and N-methyl-N-phenylsulfamoyl groups. It
is preferably an optionally substituted sulfamoyl group having from 2 to
37 carbon atoms.
The heterocyclic group bonding to the formula via a nitrogen atom, for
Z.sub.a2, includes, for example, 1-pyrrolyl, 1-imidazolyl, 1-pyrazolyl,
2-indolyl, 1-indolyl and 7-purinyl groups. It is a preferably a
heterocyclic group forming an aromatic ring. The aromatic group and the
heterocyclic group for R.sub.d3, R.sub.d4 and R.sub.d5 and the aliphatic
group for R.sub.d5 have the same meanings as the aromatic group, the
heterocyclic group and the aliphatic group, respectively, for R.sub.a1 and
R.sub.a2.
The aliphatic group for R.sub.b1 has the same meaning as the aliphatic
group for R.sub.a1 and R.sub.a2. The halogen atom for Z.sub.b1 includes,
for example, chlorine, bromine and iodine atoms.
Z.sub.c1 is referred to. The acyl group, the carbamoyl group, the sulfamoyl
group and the sulfonyl group have the same meanings as those for R.sub.a2.
The aliphatic-oxycarbonyl group includes, for example, methoxycarbonyl,
ethoxycarbonyl, i-propoxycarbonyl, benzyloxycarbonyl,
cyclohexyloxycarbonyl, n-hexadecyloxycarbonyl, allyloxycarbonyl and
pentadecenyloxycarbonyl groups. Preferably, it is an optionally
substituted alkyloxycarbonyl group having from 2 to 31 carbon atoms. The
aromatic-oxycarbonyl group includes, for example, phenyloxycarbonyl and
naphthyloxycarbonyl groups. Preferably, it is an optionally substituted
phenyloxycarbonyl group having from 7 to 37 carbon atoms. The aliphatic
group, the aromatic group and the heterocyclic group for R.sub.c1,
R.sub.c2 and R.sub.c3 have the same meaning as the aliphatic group, the
aromatic group and the heterocyclic group, respectively, for R.sub.a1 and
R.sub.a2.
The aliphatic group and the aromatic group for R.sub.d1 to R.sub.d10 and
R.sub.d12 and the heterocyclic group for R.sub.d2 to R.sub.d9 and
R.sub.d12 have the same meanings as the aromatic group, the heterocyclic
group and the aliphatic group for R.sub.a1 and R.sub.a2. The atom or
atomic group of forming an inorganic or organic salt for Y includes, for
example, Li, Na, K, Ca, Mg, triethylamine, methylamine and ammonia. The
acyl group and the sulfonyl group for R.sub.d4, R.sub.d5, R.sub.d7 and
R.sub.d8 have the same meanings as those for R.sub.a2 ; and the
aliphatic-oxycarbonyl group for Rd.sub.4, Rd.sub.5, Rd.sub.7 and Rd.sub.8
has the same meaning as that for Z.sub.c1. The ureido group for R.sub.d4,
R.sub.d5, R.sub.d7 and R.sub.d8 includes, for example, phenylureido,
methylureido, N,N-dibutylureido and N-phenyl-N-methyl-N'-methylureido
groups. It is preferably an ureido group having from 2 to 37 carbon atoms.
The urethane group for the same includes, for example, methylurethane and
phenylurethane groups. It is preferably an urethane group having from 2 to
37 carbon atoms.
The acyl group for R.sub.d6 has the same meaning as that for R.sub.a2. The
aliphatic-oxycarbonyl group and the aromatic-oxycarbonyl group for
R.sub.d6 has the same meanings as those for Z.sub.c1.
The aliphatic amino group for R.sub.d6 includes, for example, methylamino,
diethylamino, octylamino, benzylamino, cyclohexylamino, dodecylamino,
allylamino and hexadecylamino group. It is preferably an optionally
substituted alkylamino group having from 1 to 30 carbon atoms. The
aromatic amino group for R.sub.d6 includes, for example, anilino,
2,4-dichloroanilino, 4-t-octylanilino, N-methylanilino, 2-methylanilino
and N-hexadecylanilino groups. Preferably, it is an optionally substituted
anilino group having from 6 to 37 carbon atoms. The aliphatic-oxy group
for R.sub.d6 includes, for example, methoxy, ethoxy, t-butyloxy, benzyloxy
and cyclohexyloxy groups. Preferably, it is an optionally substituted
alkoxy group having from 1 to 30 carbon atoms. The aromatic-oxy group for
the same includes, for example, phenoxy, 2,4-di-t-butylphenoxy,
2-chlorophenoxy and 4-methoxyphenoxy groups. It is preferably an
optionally substituted phenoxy group having from 6 to 37 carbon atoms.
The halogen atom for R.sub.d10 includes, for example, chlorine, bromine and
iodine atoms. The acyloxy group for R.sub.d10 includes, for example,
acetyloxy and benzoyloxy groups. It is preferably an optionally
substituted acyloxy group having from 2 to 37 carbon atoms. The sulfonyl
group for R.sub.d10 has the same meaning as that for R.sub.a2.
The hydrolyzable group for R.sub.d11 includes, for example, an acyl group,
a sulfonyl group, an oxalyl group and a silyl group.
The compounds of formulae (A) to (C) are preferably those having a
secondary reaction speed constant k.sub.2 (at 80.degree. C.) with
p-anisidine, which is measured by the method described in JP-A 63-158545,
of falling within the range of from 1.times.10.sup.-5 liter/mol.sec to 1.0
liter/mol.sec.
Of the compounds of formula (D), those where R.sub.d1 is an aromatic group
are preferred. In formula (D), when Z.sub.d1 is --SO.sub.2 Y and Y is a
hydrogen atom, or an atom or atomic group of forming an inorganic or
organic salt, then it is preferred that R.sub.d1 is a phenyl group and
that the sum of the Hammett's .sigma. values of the substituent --SO.sub.2
Y on the phenyl group is 0.5 or more. In this case, the .sigma.p value may
be substituted for the .sigma.o value.
Of the compounds of formulae (A) to (D), preferred are those of formulae
(A) and (D).
Of the compounds of formula (A), those of the following formulae (A-I) to
(A-V) are preferred.
##STR115##
In formulae (A-I) to (A-V), Re.sub.1 has the same meaning as R.sub.a1 in
formula (A); Le.sub.1 represents a single bond or --O--; Le.sub.2
represents --O-- or --S--; Ar represents an aromatic group; Re.sub.2 to
Re.sub.4 may be the same or different and each represents a hydrogen atom,
an aliphatic group, an aromatic group, a heterocyclic group, an
aliphatic-oxy group, an aromatic-oxy group, a heterocyclic-oxy group, an
aliphatic-thio group, an aromatic-thio group, a heterocyclic-thio group,
an amino group, an aliphatic amino group, an aromatic amino group, a
heterocyclic amino group, an acyl group, an amido group, a sulfonamido
group, a sulfonyl group, an aliphatic-oxycarbonyl group, an
aromatic-oxycarbonyl group, a sulfo group, a carboxyl group, a formyl
group, a hydroxyl group, an acyloxy group, an ureido group, an urethane
group, a carbamoyl group or a sulfamoyl group; and at least two of
Re.sub.2 to Re.sub.4 may be bonded to each other to form a 5-membered to
7-membered ring; Ze.sub.1 and Ze.sub.2 each represent a non-metallic
atomic group necessary for forming a 5-membered to 7-membered ring;
Ze.sub.3 represents a non-metallic atomic group necessary for forming a
5-membered to 7-membered aromatic ring; the rings to be formed by Ze.sub.1
to Ze.sub.3 may optionally have substituent(s), or may form spiro rings or
bicyclo rings or may be condensed with benzene ring(s), alicyclic ring(s)
or heterocyclic ring(s).
Of the compounds of formulae (A-I) to (A-V), those of formulae (A-I) and
(A-III) are preferred.
Specific examples of these compounds are mentioned below, which, however,
are not limitative.
##STR116##
These compounds may be produced by the methods described in JP-A 62-143048,
63-115855, 63-115866, 63-158545, European Patent 255722, or by methods
similar to them.
The preferred compounds mentioned above include the compounds concretely
illustrated in the above-mentioned patent publications and also in JP-A
62-17665, 62-283338, 62-229145, 64-86139, 1-271748, Japanese Disclosure
Bulletin 90-9416 (issued by the Invention Society of Japan).
The amount of the above-mentioned compound of formulae (A) to (C) to be
used in the present invention varies, depending upon the kind of the
coupler used. In general, it may be from 0.5 to 300 mol %, preferably from
1 to 200 mol %, most preferably from 5 to 150 mol %, relative to one mol
of the coupler used.
The amount of the above-mentioned compound of formula (D) to be used in the
present invention varies, depending upon the kind of the coupler used. In
general, it may be from 0.01 to 200 mol %, preferably from 0.05 to 150 mol
%, most preferably from 0.1 to 150 mol %, relative to one mol of the
coupler used.
The above-mentioned compounds of formulae (A) to (D) are especially
preferably used along with the couplers of formula (Ia) as their
co-emulsions.
The above-mentioned compounds of formulae (A) to (D) may be used along with
known anti-fading agents, whereby the anti-fading effect is much
increased. Two or more of the compounds of formulae (A) to (D) may also be
used, as combined.
As known anti-fading agents usable in the present invention, typically
mentioned are hindered phenols such as hydroquinones, 6-hydroxychromans,
5-hydroxycoumarans, spirochromans, p-alkoxyphenols and bisphenols, as well
as gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered
amines, ultraviolet absorbents, and also ether or ester derivatives to be
obtained by silylating or alkylating the phenolic hydroxyl group of these
compounds. In addition, also usable are metal complexes such as
(bis-salicylaldoximato)nickel complexes and
(bis-N,N-dialkyldithiocarbamato)nickel complexes.
As examples of organic anti-fading agents usable in the present invention,
mentioned are hydroquinones such as those described in U.S. Pat. Nos.
2,360,290, 2,418,613, 2,700,453, 2,701,197, 2,728,659, 2,732,300,
2,735,765, 3,982,944, 4,430,425, British Patent 1,363,921, U.S. Pat. Nos.
2,710,801, 2,816,028, etc.; 6-hydroxychromans, 5-hydroxycoumarans and
spirochromans, such as those described in U.S. Pat. Nos. 3,432,300,
3,573,050, 3,574,627, 3,698,909, 3,764,337, JP-A 52-152225; spiroindanes
such as those described in U.S. Pat. No. 4,360,589; p-alkoxyphenols such
as those described in U.S. Pat. No. 2,735,765, British Patent 2,066,975,
JP-A 59-10539, JP-B 57-19765; hindered phenols such as those described in
U.S. Pat. Nos. 3,700,455, 4,228,235, JP-A 52-72224, JP-B 52-6623; gallic
acid derivatives such as those described in U.S. Pat. No. 3,457,079;
methylenedioxybenzenes such as those described in U.S. Pat. No. 4,332,886;
aminophenols such as those described in JP-B 56-21144; hindered amines
such as those described in U.S. Pat. Nos. 3,336,135, 4,268,593, British
Patents 1,326,889, 1,354,313, 1,410,846, JP-B 51-1420, JP-A 58-114036,
59-53846, 59-78344; and metal complexes such as those described in U.S.
Pat. Nos. 4,050,938, 4,241,155, British Patent 2,027,731(A).
The cyan couplers of the present invention and the above-mentioned
oil-soluble compounds can be introduced into the photographic material by
various known dispersion methods. Preferred is an oil-in-water dispersion
method in which the coupler or the compound is dissolved in a high boiling
point organic solvent (if desired, along with a low boiling point organic
solvent) and the resulting solution is dispersed in an aqueous gelatin
solution by emulsification and added to a silver halide emulsion.
Examples of high boiling point solvents to be used in an oil-in-water
dispersion method which may be employed in the present invention are
described in U.S. Pat. No. 2,322,027. As one polymer dispersion method,
known is a latex dispersion method which may also be employed in the
present invention. The process of such a latex dispersion method, the
effect of the same and specific examples of latexes for impregnation to be
used in the method are described in U.S. Pat. No. 4,199,363, German Patent
OLS Nos. 2,541,274 and 2,541,230, JP-B 53-41091 and European Patent
Laid-Open No. 029104. A dispersion method of using organic solvent-soluble
polymers may also be employed in the present invention, which is described
in PCT Laid-Open WO88/00723.
As examples of high boiling point organic solvents usable in the
above-mentioned oil-in-water method, there are mentioned phthalates (e.g.,
dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate,
di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl)
isophthalate, bis(1,1-diehtylpropyl)phthalate), phosphates or phosphonates
(e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate,
2-ethylhexyldiphenyl phosphate, dioctylbutyl phosphate, tricyclohexyl
phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate,
di-2-ethylhexylphenyl phosphate), benzoates (e.g., 2-ethylhexyl benzoate,
2,4-dichlorobenzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate),
amides (e.g., N,N-diethyldodecanamide, N,N-diethyllaurylamide), alcohols
or phenols (e.g., isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic
esters (e.g., dibutoxyethyl succinate, di-2-ethylhexyl succinate,
2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl
lactate, trioctyl citrate), aniline derivatives (e.g.,
N,N-dibutyl-2-butoxy-5-tert-octylaniline), chlorinated paraffins (e.g.,
paraffins having chlorine content of from 10% to 80%), trimesates (e.g.,
tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols
(e.g., 2,4-di-tert-amylphenol, 4-dodecyloxyphenol,
4-dodecyloxycarbonylphenol 4-(4-dodecyloxyphenylsulfonyl) phenol),
carboxylic acids (e.g., 2-(2,4-di-tert-amylphenoxybutyric acid,
2-ethoxyoctanedecanoic acid), and alkylphosphoric acids (e.g.,
di-(2-ehtylhexyl)phosphoric acid, diphenylphosphoric acid). As auxiliary
solvents usable along with the high boiling point organic solvents, there
are mentioned, for example, organic solvents having a boiling point of
approximately from 30.degree. C. to 160.degree. C., such as ethyl acetate,
butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
2-ethoxyethyl acetate, and dimethylformamide.
The proportion of the high boiling point organic solvent to be used in this
case may be from 0 to 2.0 times, preferably from 0 to 1.0 time, by weight
to the coupler.
The pH value of the film coated on the silver halide color photographic
material of the present invention must be from 4.0 to 6.5, preferably from
5.0 to 6.0. If it is higher than 6.5, the pressure resistance of the
material will be bad; but if it is lower than 4.0, such will cause a
problem in that the hardening of the material is retarded. The pH value of
the film as referred to herein means that of the film composed of all the
photographic layers to be formed by coating all the necessary coating
compositions on the support. Therefore, it does not always correspond to
the pH value of the coating compositions.
The pH value of the film in question may be measured by the method
described in JP-A 61-245153, which is as follows:
The method comprises (1) dropping 0.05 cc of pure water onto the
light-sensitive surface of the material coated with silver halide
emulsions, followed by (2) measuring the pH value of the coated film with
a film pH-measuring electrode device (GS-165F Model, made by Toa Dempa
Co.) after 3 minutes.
The adjustment of the pH value of the film may be effected by adding, if
desired, an acid (e.g., sulfuric acid, citric acid) or an alkali (e.g.,
sodium hydroxide, potassium hydroxide), to the coating compositions.
As the silver halide grains for use in the present invention, preferred are
silver chloride, silver chlorobromide or silver chloroiodobromide grains
having a silver chloride content of 95 mol % or more. Especially preferred
are silver chlorobromide or silver chloride grains substantially not
containing silver iodide, in order to shorten the developing time for
processing the photographic material. Silver halide grains substantially
not containing silver iodide as referred to herein means those having a
silver iodide content of 1 mol % or less, preferably 0.2 mol % or less. On
the other hand, in order to increase the high intensity sensitivity, to
increase the color-sensitized sensitivity or to improve the storage
stability of the photographic material, high-silver chloride grains
containing from 0.01 to 3 mol % of silver iodide on their surfaces, such
as those described in JP-A 3-84545 may also be preferably used as in some
case. Regarding the halogen composition of grains of constituting an
emulsion for use in the present invention, the grains may have different
halogen compositions. Preferably, however, the emulsion contains grains
each having the same halogen composition, as the property of the grains
may easily be homogenized. Regarding the halide composition distribution
of the grains of constituting a silver halide emulsion for use in the
present invention, the grain may have a so-called uniform halogen
composition structure where any part of the grain has the same halogen
composition; or the grain may have a so-called laminate (core/shell)
structure where the halogen composition of the core of the grain is
different from that of the shell of the same; or the grain may have a
composite halogen composition structure where the inside or surface of the
grain has a non-layered different halogen composition part (for example,
when such a non-layered different halogen composition part is on the
surface of the grain, it may be on the edge, corner or plane of the grain
as a conjugated structure). Any of such halogen compositions may properly
be selected. In order to obtain a high sensitivity photographic material,
the latter laminate or composite halogen composition structure grains are
advantageously employed, rather than the first uniform halogen composition
structure grains. Such laminate or composite halogen composition structure
grains are also preferred for preventing generation of pressure marks. In
the case of laminate or composite halogen composition structure grains,
the boundary between the different halogen composition parts may be a
definite one or may also be an indefinite one of forming a mixed crystal
structure because of the difference in the halogen compositions between
the adjacent parts. If desired, the boundary between them may positively
have a continuous structure variation.
The high-silver chloride grains for use in the present invention are
preferably those having layered or non-layered, localized phases of silver
bromide in the inside and/or on the surface of the silver halide grain, in
the manner as mentioned above. The halide composition in the localized
phase is preferably such that the phase has a silver bromide content of at
least 10 mol %, more preferably higher than 20 mol %. The silver bromide
content in the localized phase may be analyzed by X-ray diffraction (for
example, described in Lecture on New Experimental Chemistry, No. 6,
Analysis of Structure, edited by Japan Chemical Society, published by
Maruzen Publishing Co.). The localized phase may be in the inside of the
grain and/or on the edges, corners and/or planes of the surface of the
grain. As one preferred example, mentioned is an embodiment where the
localized phase has grown on the corners of the grain by epitaxial growth.
In order to reduce the amount of the replenisher to the developer to be
used in processing the photographic material of the present invention, it
is effective to further increase the silver chloride content in the silver
halide emulsions constituting the material. In this case, preferably used
are almost pure silver chloride emulsions having a silver chloride content
of from 98 mol % to 100 mol %.
The silver halide grains of constituting the silver halide emulsion of the
present invention may have a mean grain size of preferably from 0.1 .mu.m
to 2 .mu.m. (The grain size indicates a diameter of a circle having an
area equivalent to the projected area of the grain, and the mean grain
size indicates a number average value to be obtained from the measured
grain sizes.)
Regarding the grain size distribution of the emulsion, a so-called
monodispersed emulsion having a fluctuation coefficient (to be obtained by
dividing the standard deviation of the grain size distribution by the mean
grain size) of being 20% or less, preferably 15% or less, more preferably
10% or less is preferred. For the purpose of obtaining a broad latitude,
two or more monodispersed emulsions may be blended to form a mixed
emulsion for one layer, or they may be separately coated to form plural
layers. Such blending or separate coating is preferably effected for this
purpose.
Regarding the shape of the silver halide grains of constituting the
photographic emulsion of the present invention, the grains may be regular
crystalline ones such as cubic, tetradecahedral or octahedral crystalline
ones, or irregular crystalline ones such as spherical or tabular
crystalline ones, or may be composite crystalline ones composed of such
regular and irregular crystalline ones. Mixtures of grains having
different crystal forms may also be used in the present invention. Of
these, preferred are mixtures containing the above-mentioned regular
crystalline grains in a proportion of 50% or more, preferably 70% or more,
more preferably 90% or more.
Apart from these, silver halide emulsions containing tabular grains having
a mean aspect ratio (circle-corresponding diameter/thickness) of 5 or
more, preferably 8 or more, in a proportion of 50% or more of the total
grains in terms of their projected areas are also preferably used in the
present invention.
The silver (bromo)chloride emulsions for use in the present invention may
be prepared, for example, by the methods described in P. Glafkides, Chemie
et Phisique Photographique (published by Paul Montel, 1967); G. F. Duffin,
Photographic Emulsion Chemistry (published by Focal Press, 1966); and V.
L. Zelikman et al., Making and Coating Photographic Emulsion (published by
Focal Press, 1964). Briefly, they may be prepared by any of acid methods,
neutral methods and ammonia methods. As the system of reacting soluble
silver salts and soluble halides, employable is any of a single jet
method, a double jet method and a combination of them. Also employable is
a so-called reversed mixing method where silver halide grains are formed
in an atmosphere having excess silver ions. As one system of a double jet
method, employable is a so-called controlled double jet method, in which
the pAg in the liquid phase where silver halide grains are being formed is
kept constant. According to this method, silver halide emulsions
comprising regular crystalline grains having nearly uniform grain sizes
may be obtained.
It is preferred that the localized phase or the base of the silver halide
grain of the present invention contains heterologous metal ions or complex
ions. As preferred metal ions for this use, mentioned are metal ions
belonging to the Group VIII and the Group IIb of the Periodic Table and
their complexes, as well as lead ion and thallium ion. Specifically, the
localized phase may contain ions chosen from among iridium ion, rhodium
ion and iron ions and their complex ions while the base may contain ions
chosen from among osmium ion, iridium ion, rhodium ion, platinum ion,
ruthenium ion, palladium ion, cobalt ion, nickel ion and iron ion and
their complex ions, optionally as combined. The localized phase and the
base in one grain may have different contents of different metal ions.
They may contain a plurality of such metal ions and complex ions. In
particular, it is preferred that the localized phase of silver bromide
contains iron and iridium compounds.
Compounds donating such metal ions may be incorporated into the localized
phase and/or the other part (base) of the silver halide grains of the
present invention, for example, by adding the compound to an aqueous
gelatin solution which is to be a dispersing medium, or to an aqueous
halide solution, an aqueous silver salt solution or other aqueous
solutions at the step of forming the silver halide grains, or in the form
of fine silver halide grains containing the metal ions which are dissolved
in the system from which the silver halide grains are formed.
The incorporation of the metal ions into the silver halide grains of the
present invention may be effected before, during or just after the
formation of the grains. The time when the incorporation is effected may
be determined, depending on the position of the grain into which the metal
ion shall be incorporated.
The silver halide emulsions for use in the present invention is generally
subjected to chemical sensitization and color sensitization.
The chemical sensitization includes, for example, chalcogen sensitization
using a chalcogen sensitizing agent (such as typically sulfur
sensitization using unstable sulfur compounds, selenium sensitization
using selenium compounds, tellurium sensitization using tellurium
compounds), noble metal sensitization (such as typically gold
sensitization) and reduction sensitization, which may be employed singly
or as combined. As the compounds to be used for such chemical
sensitization, for example, preferred are those described in JP-A
62-215272, from page 18, right bottom column to page 22, right top column.
To more effectively attain the effect of the present invention,
gold-sensitized, high-silver chloride emulsions are used in the present
invention.
The emulsions to be used in the present invention are so-called surface
latent image-type emulsions which form latent images essentially on the
surfaces of the grains.
The silver halide emulsions for use in the present invention may contain
various compounds or precursors, for the purpose of preventing the
photographic material from being fogged during preparation, storage or
photographic processing of the material and of stabilizing the
photographic properties of the material. Specific examples of such
compounds which are preferably used in the present invention are described
in the above-mentioned JP-A 62-215272, pages 39 to 72. In addition, the
5-arylamino-1,2,3,4-thiatriazole compounds (where the aryl residue has at
least one electron-attracting group) described in EP 0447647 are also
preferably used in the present invention.
The color sensitization is effected so as to make the emulsions of the
layers constituting the photographic material of the present invention
sensitive to light falling within a desired wavelength range.
For the color sensitization, used are color-sensitizing dyes effective in
making photographic emulsions sensitive to blue, green and red ranges.
Such are described in, for example, F. M Harmer, Heterocyclic
Compound--Cyanine Dyes and Related Compounds (John Wiley & Sons, New York,
London, 1964). Specific examples of color-sensitizing compounds as well as
color-sensitizing methods which are preferably employed in the present
invention are described in, for example, the above-mentioned JP-A
62-215272, from page 22, right top column to page 38. In particular, the
color-sensitizing dyes described in JP-A 3-123340 are especially preferred
as red-sensitizing dyes to be applied to silver halide grains having a
high silver chloride content, in view of the high stability of the dyes
themselves, the high intensity of adsorption of the dyes to silver halide
grains, and the low temperature dependence of the dyes during exposure of
photographic materials.
Where the photographic material of the present invention is desired to be
made highly sensitive to infrared range, preferably used are the
sensitizing dyes described in JP-A 3-15049, from page 12, left top column
to page 21, left bottom column; JP-A 3-20730, from page 4, left bottom
column to page 15, left bottom column; EP 0420011, from page 4, line 21 to
page 6, line 54; EP 0420012, from page 4, line 12 to page 10, line 33; and
EP 0443466, U.S. Pat. No. 4,975,362.
To incorporate these color-sensitizing dyes into the silver halide
emulsions of the present invention, for example, they may be directly
dispersed thereinto, or alternatively, they are first dissolved in a
single solvent such as water, methanol, ethanol, propanol, methyl
cellosolve, 2,2,3,3-tetrafluoropropanol, etc. or a mixed solvent
comprising them, and thereafter the resulting solution may be added to the
emulsions. Alternatively, the dyes are formed into aqueous solutions in
the presence of acids or bases in the manner such as those described in
JP-B 44-23389, 44-27555, 57-22089, or are formed into aqueous solutions or
colloidal dispersion in the presence of surfactants in the manner such as
that described in U.S. Pat. Nos. 3,822,135, and 4,006,025, and the
resulting solutions or dispersions may be added to the emulsions. Also,
they may be first dissolved in solvents which are substantially immiscible
with water, such as phenoxyethanol, etc. and then dispersed in water or
hydrophilic colloids, and the resulting dispersions may be added to the
emulsions. Also, they may be directly dispersed into hydrophilic colloids
in the manner such as those described in JP-A 53-102733, 58-105141, and
the resulting dispersions may be added to the emulsions. Anyhow, the
color-sensitizing dyes may be added to the emulsions at any time when the
emulsions are prepared. In other words, the time when the dyes are added
to the emulsions may be any of before or during formation of the silver
halide grains, immediately after formation of them and before rinsing
them, before or during chemical sensitization of them, immediately after
chemical sensitization of them and before cooling and solidifying them,
and during preparation of coating compositions. More generally, the dyes
are added to the emulsions after chemical sensitization of the emulsions
and before coating them. If desired, however, the dyes may be added to the
emulsions along with chemically-sensitizing dyes so as to effect the color
sensitization and the chemical sensitization of the emulsions at the same
time, in the manner such as that described in U.S. Pat. Nos. 3,628,969,
and 4,225,666; or the dyes may be added to the emulsions prior to the
chemical sensitization of the emulsions in the manner such as that
described in JP-A 58-113928; or the color sensitization of the emulsions
may be started before the completion of the formation of precipitates of
silver halide grains. In addition, it is also possible to divide the
color-sensitizing dye to be added into plural parts, which are added to
the emulsions at several times, in the manner such as that taught by U.S.
Pat. No. 4,225,666. According to the process, a part of the
color-sensitizing dye is added to the emulsions prior to the chemical
sensitization of them and the remaining part thereof is added thereto
after the chemical sensitization. The addition of the color-sensitizing
dyes to the photographic emulsions may be effected at any time when the
silver halide grains are formed, for example, in accordance with the
process taught by U.S. Pat. No. 4,183,756. Of the above-mentioned methods,
especially preferred is the method where the dyes are added to the
emulsions before the step of rinsing the emulsions or before the step of
chemically sensitizing them.
The amount of the color-sensitizing dye to be added varies in a broad
range, depending on the case of using it. Preferred is the range of from
0.5.times.10.sup.-6 mol to 1.0.times.10.sup.-2 mol, more preferably from
1.0.times.10.sup.-6 mol to 5.0.times.10.sup.-3 mol, relative to one mol of
the silver halide to which the dye is added.
When the photographic material of the present invention contains
color-sensitizing dyes capable of making it sensitive to light falling
within a red to infrared range, it is preferred to incorporate into the
photographic material the compounds described in JP-A 2-157749, from page
13, right bottom column to page 22, right bottom column, along with the
dyes. Using these compounds, the storability of the photographic material,
the stability during processing the material and the
supercolor-sensitizing effect of the material may be specifically
improved. Above all, the compounds of formulae (IV), (V) and (VI)
described in said patent publication are especially preferred. The
compound is added to the photographic material in an amount of from
0.5.times.10.sup.-5 mol to 5.0.times.10.sup.-2 mol, preferably from
5.0.times.10.sup.-5 mol to 5.0.times.10.sup.-3 mol, relative to one mol of
the silver halide in the material. The preferred range of the amount of
the compound to be added is from 0.1 to 10000 molar times, preferably from
0.5 to molar 5000 times the sensitizing dye to be combined with the
compound.
The photographic material of the present invention may be applied to a
printing system using an ordinary negative printer. In addition to this,
the material is also preferably applied to digital scanning exposure using
monochromatic high-density lights such as gas lasers, light-emitting
diodes, semiconductor lasers, secondary high-harmonics generating light
sources (SHG) comprising a combination of a semiconductor laser or a solid
laser where a semiconductor laser is used as an exciting light source and
non-linear optical crystals, etc. In order to make the system compact and
low-priced, use of semiconductor lasers or secondary high-harmonics
generating light sources (SHG) comprising a combination of a semiconductor
laser or solid laser and non-linear optical crystals is preferred. In
particular, in order to design a low-priced, long-life and highly-safe
device, use of semiconductor lasers is preferred, and it is desired to use
a semiconductor laser as at least one light source for exposure.
When the above-mentioned light sources for scanning exposure are used, the
maximum color sensitivity of the photographic material of the present
invention may be freely defined, depending on the wavelength of the light
source to be used for scanning exposure of the material. Using SHG light
sources to be obtained by combining a solid laser where a semiconductor is
used as the exciting light source or a semiconductor and non-linear
optical crystals, the oscillating wavelength of the laser may be halved so
that blue light and green light may be obtained. Therefore, the maximum
color sensitivity of the photographic material to be exposed with such
light sources may fall within ordinary ranges of three colors of blue,
green and red. When semiconductor lasers are used as light sources so as
to make the exposure device low-priced, highly-safe and compact, it is
preferred that at least two layers constituting the photographic material
to be exposed to them have a maximum color sensitivity at 670 nm or
longer. This is because the wavelength range of the light to be emitted by
low-priced and stable III-V Groups semiconductor lasers which are
available at present is only from red to infrared range. In a laboratory
level, however, oscillation of II-VI Groups semiconductor lasers in green
to blue range has been confirmed. Therefore, it is surely expected that
such semiconductor lasers may be used stably at low costs, after further
development of the technique of producing such semiconductor lasers. If
so, the necessity of making the photographic material have at least two
photographic emulsion layers that have a maximum color sensitivity at 670
nm or longer will be neglected.
In such scanning exposure, the period of time for which the silver halides
in the photographic material are exposed means the period of time for
which a certain small area of the material is exposed. As the small area,
generally used is the minimum unit for which the quantity of light is
controlled from the corresponding digital data. The minimum unit is
referred to as a pixel. Therefore, the exposure time per pixel shall be
varied, depending on the size of pixel. The size of pixel depends on the
pixel density, and its actual range is from 50 to 2000 dpi. Where the
exposure time is defined to be such that one pixel having a pixel density
of 400 dpi is exposed for the defined time, the preferred exposure time
may be 10.sup.-4 second or less, more preferably 10.sup.-6 second or less.
The photographic material of the present invention preferably contains dyes
which are decolored by photographic processing, such as those described in
EP 0337490A2, pages 27 to 76, especially oxonole dyes or cyanine dyes, in
its hydrophilic colloid layers, for the purpose of anti-irradiation and
anti-halation and of improving the safety of the material against
safelight.
Some of these water-soluble dyes often worsen the color separation of
processed photographic materials or the safety thereof against safelight,
if their amounts added are increased. As dyes which can be used without
worsening the color separation of processed photographic materials,
preferred are the water-soluble dyes described in JP-A 5-127324, 5-127325
and 5-216185.
The photographic material of the present invention may have a colored
layer, in place of or along with the water-soluble dyes, which may be
decolored while the material is processed. The colored layer to be used,
which may be decolored while the photographic material is processed, may
be kept in direct contact with the emulsion layers or may be disposed in
the material in such a way that it is kept in indirect contact with the
emulsion layers via an interlayer containing gelatin or a color mixing
preventing agent such as hydroquinone. It is preferred that the colored
layer is disposed below the emulsion layer (nearer to the support than the
emulsion layer), which colors to give a primary color of the same kind as
the color of the colored layer. It is possible either to dispose the
corresponding colored layer below each of all the emulsion layers in
accordance with the primary color to be yielded by each emulsion layer or
to dispose it below some of those freely selected from the emulsion
layers. It is also possible to dispose a colored layer corresponding to
plural emulsion layers yielding different colors. It is preferred that the
optical reflective density of the colored layer falls from 0.2 to 3.0,
more preferably from 0.5 to 2.5, especially preferably from 0.8 to 2.0, at
the wavelength of the highest optical density in the wavelength range of
the light to be used for exposing the photographic material. (The
wavelength range is the range of visible rays, which is from 400 nm to 700
nm, for ordinary printer exposure, while, for scanning exposure, it
corresponds to the wavelength range of the light source to be used for
scanning exposure.)
To provide the colored layer in the photographic material of the present
invention, any known method may be employed. For instance, employable are
a method of incorporating a dispersion of fine grains of a solid dye, such
as those described in JP-A 2-282244, from page 3, right top column to page
8 and those described in JP-A 3-7931, from page 3, right top column to
page 11, left bottom column, into a hydrophilic colloid layer; a method of
mordanting a cationic polymer with an anionic dye; a method of making a
dye adsorb to fine grains of silver halides, etc. to thereby fix the dye
in the colored layer; and a method of using a colloidal silver such as
that described in JP-A 1-239544. As the method of dispersing fine grains
of a solid dye into a hydrophilic colloid layer, for example, JP-A
2-308244 has disclosed, on pages 4 to 13, a method of incorporating fine
grains of a dye which is substantially insoluble in water at least at pH 6
or lower but is substantially soluble in water at least at pH 8 or higher,
into a colloid layer. One example of the method of mordanting a cationic
polymer with an anionic dye has been described in JP-A 2-84637, pages 18
to 26. Methods for preparing colloidal silvers, which act as a
light-absorbing agent, are disclosed in U.S. Pat. Nos. 2,688,601 and
3,459,563. Of these methods, preferred are the method of incorporating
fine dye grains and the method of using a colloidal silver.
As the binder or protective colloid which may be used in the photographic
material of the present invention, gelatin is preferred but any other
hydrophilic colloid may also be used singly or along with gelatin. As the
gelatin, preferred is a low-calcium gelatin having a calcium content of
800 ppm or less, more preferably 200 ppm or less. In order to prevent the
growth of various fungi or bacteria, which grow in hydrophilic colloid
layers to worsen the image quality of the images to be formed, it is
preferred to add a fundicidal agent such as that described in JP-A
63-271247 to the hydrophilic colloid layers constituting the photographic
material of the present invention.
Where the photographic material of the present invention is subjected to
printer exposure, it is preferred to use a band-stop filter such as those
described in U.S. Pat. No. 4,880,726. Using this, color mixing may be
inhibited so that the color reproducibility of the photographic material
is noticeably improved.
The exposed photographic material of the present invention is processed
according to conventional color development. To rapidly process it, the
material is, after having been subjected to color development, preferably
blixed. In particular, when the material contains the above-mentioned
high-silver chloride emulsions, the pH value of the blixer to be used is
preferably about 6.5 or less, more preferably about 6 or less, so as to
promote the desilvering of the material.
As silver halide emulsions and other elements (e.g., additives, etc.) of
constituting the photographic material of the present invention,
photographic layers of constituting the material (e.g., arrangement of
layers), and methods of processing the material and additives usable in
the processing methods, those described in the following patent
publications, especially in European Patent 0,355,660A2 (corresponding to
JP-A 2-139544), are preferably employed.
__________________________________________________________________________
Photographic Elements
JP-A 62-215272 JP-A 2-33144 EP 0,355,660A2
__________________________________________________________________________
Silver Halide Emulsions
From page 10, right upper
From page 28, right upper
From page 45, line 53 to
page
column, line 6 to page 12, left
column, line 16 to page
47, line 3; and page 47,
lines
lower column, line 5; and
right lower column, line
20 to 22
from page 12, right lower
and page 30, lines 2 to 5
column, line 4 to page 13, left
upper column, line 17
Silver Halide Solvents
Page 12, left lower column,
-- --
lines 6 to 14; and from page
13, left upper column, line 3
from below to page 18, left
lower column, last line
Chemical Sensitizers
Page 12, from left lower
Page 29, right lower column,
Page 47, lines 4 to 9
column, line 3 from below to
line 12 to last line
right lower column, line 5
from below; and from page
18, right lower column, line 1
to page 22, right upper
column, line 9 from below
Color Sensitizers
From page 22, right upper
Page 30, left upper column,
Page 47, lines 10 to 15
(Color Sensitizing Methods)
column, line 8 from below to
lines 1 to 13
page 38, last line
Emulsion Stabilizers
From page 39, left upper
Page 30, from left upper
Page 47, lines 16 to 19
column, line 1 to page 72,
column, line 14 to right
right upper column, last line
upper column, line 1
Development Promoters
From page 72, left lower
-- --
column, line 1 to page 91,
right upper column, line 3
Color Couplers (Cyan,
From page 91, right upper
From page 3, right upper
Page 4, lines 15 to 27;
from
Magenta and Yellow
column, line 4 to page 121,
column, line 14 to page
page 5, line 30 to page
8, last
Couplers) left upper column, line 6
left upper column, last
line; page 45, lines 29
to 31;
and from page 30, right
and from page 47, line 23
to
upper column, line 6 to
page 63, line 50
35, right lower column, line
11
Coloring Enhancers
From page 121, left upper
-- --
column, line 7 to page 125,
right upper column, line 1
Ultraviolet Absorbents
From page 125, right upper
From page 37, right lower
Page 65, lines 22 to 31
column, line 2 to page 127,
column, line 14 to page 38,
left lower column, last line
left upper column, line 11
Anti-fading Agents
From page 127, right lower
From page 36, right upper
From page 4, line 30 to
page
(Color Image Stabilizers)
column, line 1 to page 137,
column, line 12 to page
5, line 23; from page 29,
line
left lower column, line 8
left upper column, line
1 to page 45, line 25;
page 45,
lines 33 to 40; and page
65,
lines 2 to 21
High Boiling Point and/or
From page 137, left lower
From page 35, right lower
Page 64, lines 1 to 51
Low Boiling Point Organic
column, line 9 to page 144,
column, line 14 to page 36,
Solvents right upper column, last line
left upper column, line 4
from below
Dispersing Methods of
From page 144, left lower
From page 27, right lower
From page 63, line 51 to
page
Photographic Additives
column, line 1 to page 146,
column, line 10 to page
64, line 56
right upper column, line 7
left upper column, last line;
and from page 35, right
lower column, line 12, to
page 36, right upper column,
line 7
Hardening Agents
From page 146, right upper
-- --
column, line 8 to page 155,
left lower column, line 4
Developing Agent
Page 155, from left lower
-- --
Precursors column, line 5 to right lower
column, line 2
Development Inhibitor
Page 155, right lower
-- --
Releasing Compounds
column, lines 3 to 9
Constitution of Photographic
Page 156, from left upper
Page 28, right upper column,
Page 45, lines 41 to 52
Layers column, line 15 to right
lines 1 to 15
lower column, line 14
Dyes From page 156, right lower
Page 38, from left upper
Page 66, lines 18 to 22
column, line 15 to page 184,
column, line 12 to right
right lower column, last line
upper column, line 7
Color Mixing Preventing
From page 185, left upper
Page 36, right upper column,
From page 64, line 57 to
page
Agents column, line 1 to page 188,
lines 8 to 11 65, line 1
right lower column, line 3
Gradation Adjusting Agents
Page 188, right lower
-- --
column, lines 4 to 8
Stain Inhibitors
From page 188, right lower
Page 37, from left upper
From page 65, line 32 to
page
column, line 9 to page 193,
column, last line to right
66, line 17
right lower column, line 10
lower column, line 13
Surfactants From page 201, left lower
From page 18, right upper
--
column, line 1 to page 210,
column, line 1 to page 24,
right upper column, last one
right lower column, last line;
and page 27, from left lower
column, line 10 from below to
right lower column, line 9
Fluorine-containing
From page 210, left lower
From page 25, left upper
--
Compounds (as antistatic
column, line 1 to page 222,
column, line 1 to page 27,
agents, coating aids,
left lower column, line 5
right lower column, line 9
lubricants, and anti-blocking
agents)
Binders (hydrophilic
From page 222, left lower
Page 38, right upper column,
Page 66, lines 23 to 28
colloids) column, line 6 to page 225,
lines 8 to 18
left upper column, last line
Tackifiers From page 225, right upper
-- --
column, line 1 to page 227,
right upper column, line 2
Antistatic Agents
From page 227, right upper
-- --
column, line 3 to page 230,
left upper column, line 1
Polymer Latexes From page 230, left upper
-- --
column, line 2 to page 239,
last line
Mat Agents Page 240, from left upper
-- --
column, line 1 to right upper
column, last line
Photographic Processing
From page 3, right upper
From page 39, left upper
From page 67, line 14 to
page
Methods (Processing steps
column, line 7 to page 10,
column, line 4 to page 42,
69, line 28
and additives) right upper column, line 5
upper column, last line
__________________________________________________________________________
The cited specification of JP-A 62-215272 is one as amended by the letter
of amendment filed on Mar. 16, 1987.
In addition to the above-mentioned couplers, so-called shortwave-type
yellow couplers such as those described in JP-A 63-231451, 63-123047,
63-241547, 1-173499, 1-213648 and 1-250944 are also preferably used.
As yellow couplers, also preferably used in the present invention are
acylacetamide yellow couplers where the acyl group has a 3-membered to
5-membered cyclic structure, such as those described in European Patent
0447969A1; malondianilide yellow couplers having a cyclic structure such
as those described in European Patent 0482552A1; and acylacetamide yellow
couplers having a dioxane structure such as those described in U.S. Pat.
No. 5,118,599, in addition to the compounds described in the
above-mentioned table. Above all, acylacetamide yellow couplers where the
acyl group is an 1-alkylcyclopropane-1-carbonyl group, and malondianilide
yellow couplers where one anilide constitutes an indoline ring are
especially preferably used. These couplers may be used singly or as
combined.
The magenta couplers usable in the present invention are 5-pyrazolone
magenta couplers and pyrazoloazole magenta couplers such as those
described in the above-mentioned patent publications. In particular,
however, especially preferred are pyrazolotriazole couplers where a
secondary or tertiary alkyl group is directly bonded to the 2, 3 or
6-position of the pyrazolotriazole ring, such as those described in JP-A
61-65245; pyrazoloazole couplers having a sulfonamido group in the
molecule, such as those described in JP-A 61-65246; pyrazoloazole couplers
having an alkoxyphenylsulfonamido ballast group, such as those described
in JP-A 61-147254; and pyrazoloazole couplers having a 6-positioned alkoxy
or aryloxy group, such as those described in European Patents 226,849A and
294,785A, in view of the color hue and the stability of images to be
formed therefrom and of the coloring property of themselves.
The color developer to be used for developing the photographic material of
the present invention preferably contains an organic preservative in place
of hydroxylamine and sulfite ion.
The organic preservative as referred to herein includes all organic
compounds which are added to processing solutions for color photographic
materials so as to retard the deterioration of the aromatic primary amine
color developing agents therein. In other words, they are organic
compounds having a function of preventing color developing agents from
being oxidized with air, etc. Above all, especially effective organic
preservatives are hydroxylamine derivatives (excluding hydroxylamine),
hydroxamic acids, hydrazines, hydrazides, .alpha.-amino acids, phenols,
.alpha.-hydroxyketones, .alpha.-aminoketones, saccharides, monoamines,
diamines, polyamines, quaternary ammonium salts, nitroxy radicals,
alcohols, oximes, diamide compounds, condensed cyclic amines, etc. These
are disclosed in JP-B 48-30496, JP-A 52-143020, 63-4235, 63-30845,
63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63-58346, 63-43138,
63-146041, 63-44657, 63-44656, U.S. Pat. Nos. 3,615,503, 2,494,903, JP-A
1-97953, 1-186939, 1-186940, 1-187557, 2-306244, European Patent Laid-Open
No. 0530921A1, etc. As other preservatives, also employable, if desired,
are various metals such as those described in JP-A 57-44148, 57-53749;
salicylic acids such as those described in JP-A 59-180588; amines such as
those described in JP-A 63-239447, 63-128340, 1-186939, 1-187557;
alkanolamines such as those described in JP-A 54-3532; polyethyleneimines
such as those described in JP-A 56-94349; and aromatic polyhydroxylamines
such as those described in U.S. Pat. No. 3,746,544. In particular,
especially preferred are alkanolamines such as triethanolamine;
dialkylhydroxylamines such as N,N-diethylhydroxylamine and
N,N-di(sulfoethyl)hydroxylamine; .alpha.-amino acid derivatives such as
glycine, alanine, leucine, serine, threonine, valine and isoleucine; and
aromatic polyhydroxyl compounds such as sodium catechol-3,5-disulfonate.
In particular, the combination of dialkylhydroxylamines and alkanolamines
and the combination of dialkylhydroxylamines such as those described in
European Patent Laid-Open No. 0530921A1, .alpha.-amino acid such as
typically glycine, and alkanolamines are especially preferably employed,
as improving the stability of color developers containing them and
especially improving the stability thereof during continuous processing
therewith.
The amount of the organic preservative to be added to developers may be
such that the preservative added may have a function to prevent the
deterioration of the color developing agent in the developer. Preferably,
it is from 0.01 to 1.0 mol/liter, more preferably from 0.03 to 0.30
mol/liter.
To process the color photographic material of the present invention, the
processing materials and the processing methods described in JP-A
2-207250, from page 26, right bottom column, line 1 to page 34, right top
column, line 9 and JP-A 4-97355, from page 5, left top column, line 17 to
page 18, right bottom column, line 20 are preferably employed, in addition
to those referred to in the above-mentioned table.
The present invention will be explained in more detail by means of the
following examples, which, however, are not intended to restrict the scope
of the present invention. In the examples, unless otherwise indicated, all
percents are by weight.
EXAMPLE 1
Preparation of Supports
Titanium dioxide was added to a low-density polyethylene having MRF of 3 at
the proportion indicated in Table 1 below, and zinc stearate was added
thereto at the proportion of 3.0% by weight to the titanium dioxide. The
resulting mixture was kneaded along with ultramarine (DV-1, product of
Dai-ichi Chemical Industry Co.) in a Bumbury's mixer and then shaped into
pellets constituting a master batch. The grain size of the titanium
dioxide used was from 0.15 .mu.m to 0.35 .mu.m, from electromicroscopic
observation. The titanium dioxide grains used herein were those coated
with aluminium oxide hydrate in an amount of 0.75% by weight, as Al.sub.2
O.sub.3, relative to titanium dioxide.
A paper base having a weight of 170 g/m.sup.2 was treated by corona
discharging at 10 kVA, and the pellets prepared above were melt-extruded
thereover at 320.degree. C. through a multi-layer coating die to form a
polyethylene laminate layer having the thickness as indicated in Table 1
below on the base. The surface of the polyethylene laminate layer was
treated by glow discharging, and then a gelatin subbing layer containing
sodium dodecylbenzenesulfonate was formed thereon.
TABLE 1
__________________________________________________________________________
Constitution of Multi-layered Waterproof Resin Laminate Layer
Uppermost Layer Interlayer Lowermost Layer
Mean TiO.sub.2
Support
TiO.sub.2 Content
Thickness
TiO.sub.2 Content
Thickness
TiO.sub.2 Content
Thickness
Content
Remarks
__________________________________________________________________________
A 15 wt. %
30.mu.
-- -- -- -- 15.0 wt. %
comparative
sample
B 25 wt. %
30.mu.
-- -- -- -- 25.0 wt. %
comparative
sample
C 10 wt. %
1.mu.
15 wt. %
28.mu.
10 wt. %
1.mu.
14.7 wt. %
sample of the
invention
D 25 wt. %
15.mu.
-- -- 0 wt. %
15.mu.
12.5 wt. %
sample of the
invention
E 25 wt. %
15.mu.
-- -- 5 wt. %
15.mu.
15.0 wt. %
sample of the
invention
F 35 wt. %
15.mu.
-- -- 0 wt. %
15.mu.
17.5 wt. %
sample of the
invention
G 35 wt. %
15.mu.
-- -- 15 wt. %
15.mu.
25.0 wt. %
sample of the
invention
H 35 wt. %
15.mu.
-- -- 25 wt. %
1.mu.
30.0 wt. %
sample of the
invention
I 10 wt. %
2.mu.
25 wt. %
26.mu.
10 wt. %
2.mu.
23.0 wt. %
sample of the
invention
__________________________________________________________________________
The TiO.sub.2 content and the mean TiO.sub.2 content as referred to in
Table 1 above indicate % by weight of TiO.sub.2 relative to the sum of
TiO.sub.2 and the resin of being 100% by weight.
Preparation of Photographic Material Samples:
Plural photographic constitutive layers each having the composition
mentioned below were coated over one of the supports obtained as above to
form a multi-layered color photographic paper (sample No. 101). The
coating liquids used here were prepared in the manner mentioned below.
Preparation of Coating Liquid for Fifth Layer:
27.2 cc of ethyl acetate, 0.50 g of solvent (Solv-1) and 7.4 g of solvent
(Solv-6) were added to 12.4 g of cyan coupler (ExC), 0.40 g of color image
stabilizer (Cpd-9), 0.40 g of color image stabilizer (Cpd-8), 7.0 g of
ultraviolet absorbent (UV-2), 9.5 g of color image stabilizer (Cpd-1),
0.40 g of color image stabilizer (Cpd-6), 0.40 g of color image stabilizer
(Cpd-10) and 0.40 g of color image stabilizer (Cpd-11) to dissolve them,
and the resulting solution was added to 270 cc of an aqueous 10% gelatin
solution containing 8 cc of sodium dodecylbenzenesulfonate and emulsified
and dispersed therein using an ultrasonic homogenizer. To the
thus-obtained dispersion, added were silver chlorobromide emulsions
R.sub.1 and R.sub.2 which were be mentioned below. These were mixed to
prepare a coating liquid for the fifth layer.
Other coating liquids for the other layers than the fifth layer were
prepared in the same manner as above. As gelatin hardening agents for each
layer, added thereto were 1-hydroxy-3,5-dichloro-s-triazine sodium salt
and 1,2-bis(vinylsulfonyl)ethane.
The layers contained 25.0 mg/m.sup.2, as a whole, of Cpd-14 and 50
mg/m.sup.2, as a whole, of Cpd-15.
The silver chlorobromide emulsions for the light-sensitive emulsion layers
constituting Sample No. 101 contained the following color-sensitizing
dyes.
Blue-sensitive Emulsion Layer:
Sensitizing Dye A:
##STR117##
(2.0.times.10.sup.-4 mol per mol of silver halide to large-size emulsion;
and 2.5.times.10.sup.-4 mol per mol of silver halide to small-size
emulsion)
Sensitizing Dye B:
##STR118##
(2.0.times.10.sup.-4 mol per mol of silver halide to large-size emulsion;
and 2.5.times.10.sup.-4 mol per mol of silver halide to small-size
emulsion)
Green-sensitive Emulsion Layer:
Sensitizing Dye C:
##STR119##
(4.0.times.10.sup.-4 mol per mol of silver halide to large-size emulsion;
and 5.6.times.10.sup.-4 mol per mol of silver halide to small-size
emulsion)
Sensitizing Dye D:
##STR120##
(7.0.times.10.sup.-5 mol per mol of silver halide to large-size emulsion;
and 1.0.times.10.sup.-4 mol per mol of silver halide to small-size
emulsion)
Red-sensitive Emulsion Layer:
Sensitizing Dye E:
##STR121##
(0.9.times.10.sup.-4 mol per mol of silver halide to large-size emulsion;
and 1.1.times.10.sup.-4 mol per mol of silver halide to small-size
emulsion)
In addition, the following compound was added in an amount of
2.6.times.10.sup.-3 mol per mol of silver halide.
##STR122##
To the blue-sensitive emulsion layer, the green-sensitive emulsion layer
and the red-sensitive emulsion layer was added
1-(5-methylureidophenyl)-5-mercaptotetrazole each in an amount of
3.4.times.10.sup.-4 mol, 9.7.times.10.sup.-4 mol and 5.5.times.10.sup.-4
mol, per mol of silver halide, respectively.
To the blue-sensitive emulsion layer and the green-sensitive emulsion layer
was added 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene each in an amount of
1.times.10.sup.-4 mol and 2.times.10.sup.-4 mol, per mol of silver halide,
respectively. For anti-irradiation, the following dyes were added to the
respective emulsion layers, the coated amount being parenthesized.
##STR123##
Layer Constitution:
Compositions of the layers of constituting sample No. 101 are mentioned
below, in which the numerical value indicates the amount coated
(g/m.sup.2) and the amount of the silver halide coated is represented as
silver therein. The pH value of the coated film was adjusted at 7.0, by
suitably controlling the pH values of the coating liquids.
Support:
Support A mentioned above.
______________________________________
First Layer: Yellow Coupler-containing Blue-sensitive
Emulsion Layer
Silver Chlorobromide Emulsion (5/5 (by mol of
0.27
silver) mixture of large-size emulsion Bl of cubic
grains with a mean grain size of 0.8 .mu.m and small-
size emulsion B2 of cubic grains with a mean grain
size of 0.5 .mu.m; the fluctuation coefficient of the
grain size distribution of the two emulsions was
0.08 and 0.09, respectively; the silver halide
grains in the both emulsions had 0.4 mol % of
silver bromide locally on a part of the surface of
each grain comprising silver chloride)
Gelatin 1.21
Yellow Coupler (ExY) 0.79
Color Image Stabilizer (Cpd-1)
0.06
Color Image Stabilizer (Cpd-2)
0.04
Color Image Stabilizer (Cpd-3)
0.08
Solvent (Solv-1) 0.10
Solvent (Solv-2) 0.16
Second Layer: Color Mixing Preventing Layer
Gelatin 0.95
Color Mixing Preventing Agent (Cpd-4)
0.08
Solvent (Solv-2) 0.20
Solvent (Solv-3) 0.25
Solvent (Solv-7) 0.01
Third Layer: Magenta Coupler-containing Green-sensitive
Emulsion Layer
Silver Chlorobromide Emulsion (6/4 (by mol of Ag)
0.13
mixture of large-size emulsion Gl of cubic grains
with a mean grain size of 0.55 .mu.m and small-size
emulsion G2 of cubic grains with a mean grain size
of 0.39 .mu.m; the two emulsions each had a
fluctuation coefficient of the grain size
distribution of 0.10 and 0.08, respectively; the
large-size emulsion contained 0.8 mol % of AgBr
locally on a part of the surface of each grain
comprising silver chloride, and the small-size
emulsion contained 1.0 mol % of AgBr locally on a
part of the surface of each grain comprising
silver chloride)
Gelatin 1.38
Magenta Coupler (ExM) 0.16
Color Image Stabilizer (Cpd-2)
0.03
Color Image Stabilizer (Cpd-5)
0.07
Color Image Stabilizer (Cpd-6)
0.01
Color Image Stabilizer (Cpd-7)
0.01
Color Image Stabilizer (Cpd-8)
0.07
Solvent (Solv-3) 0.30
Solvent (Soly-5) 0.10
Solvent (Solv-8) 0.20
Solvent (Solv-9) 0.10
Fourth Layer: Color Mixing Preventing Layer
Gelatin 0.65
Color Mixing Preventing Agent (Cpd-4)
0.06
Solvent (Solv-2) 0.15
Solvent (Solv-3) 0.18
Solvent (Solv-7) 0.01
Fifth Layer: Cyan Coupler-containing Red-sensitive
Emulsion Layer
Silver Chlorobromide Emulsion (7/3 (by mol of Ag)
0.20
mixture of large-size emulsion R1 of cubic grains
with a mean grain size of 0.58 .mu.m and small-size
emulsion R2 of cubic grains with a mean grain size
of 0.45 .mu.m; the two emulsions each had a
fluctuation coefficient of the grain size
distribution of 0.09 and 0.11, respectively; the
large-size emulsion contained 0.6 mol % of AgBr
locally on a part of the surface of each grain
comprising silver chloride, and the small-size
emulsion contained 0.8 mol % of AgBr locally on a
part of the surface of each grain comprising
silver chloride)
Gelatin 0.84
Cyan Coupler (ExC) 0.32
Ultraviolet Absorbent (UV-2) 0.18
Color Image Stabilizer (Cpd-1)
0.25
Color Image Stabilizer (Cpd-6)
0.01
Color Image Stabilizer (Cpd-8)
0.01
Color Image Stabilizer (Cpd-9)
0.01
Color Image Stabilizer (Cpd-10)
0.01
Color Image Stabilizer (Cpd-11)
0.01
Solvent (Solv-1) 0.01
Solvent (Solv-6) 0.19
Sixth Layer: Ultraviolet Absorbing Layer
Gelatin 0.53
Ultraviolet Absorbent (UV-1) 0.38
Color Image Stabilizer (Cpd-12)
0.15
Seventh Layer: Protective Layer
Gelatin 1.12
Acryl-modified Copolymer of Polyvinyl Alcohol
0.07
(modification degree 17%)
Liquid Paraffin 0.01
Color Image Stabilizer (Cpd-13)
0.01
______________________________________
The compounds used above are mentioned below.
##STR124##
Other samples (Nos. 102 to 131) were prepared in the same manner as in
preparation of sample No. 101, except that the support, the cyan coupler
and the pH value of the coated film were varied to those indicated in
Table 2 below.
Sample No. 101 was imagewise printed and then processed continuously
(running processing) according to the process mentioned below while a
replenisher mentioned below was replenished to the developer tank, until
the amount of the replenisher to the developer tank became two times the
capacity of the developer tank.
______________________________________
Process for Color Development:
Amount of
Replenisher
Processing Step
Temperature Time (*)
______________________________________
Color 35.degree. C.
45 sec 161 ml
Development
Blixation 35.degree. C.
45 sec 218 ml
Rinsing 1 35.degree. C.
30 sec --
Rinsing 2 35.degree. C.
30 sec --
Rinsing 3 35.degree. C.
20 sec 360 ml
Drying 80.degree. C.
60 sec
______________________________________
(*)per m.sup.2 of sample being processed.
(Rinsing was effected by threetank countercurrent cascade system from 3 t
1.)
Compositions of the processing solutions used above are mentioned below.
______________________________________
Tank Re-
Color Developer Solution plenisher
______________________________________
Water 800 ml 800 ,
ml
Ethylenediamine-tetraacetic Acid
3.0 g 3.0 g
Disodium 4,5-Dihydroxybenzene-1,3-
0.5 g 0.5 g
disulfonate
Triethanolamine 12.0 g 12.0 g
Potassium Chloride 2.5 g --
Potassium Bromide 0.01 g --
Potassium Carbonate 27.0 g 27.0 g
Sodium Sulfite 0.1 g 0.2 g
N-ethyl-N-(.beta.-methanesulfonamidoethyl)-3-
5.0 g 7.1 g
methyl-4-aminoaniline 3/2 Sulfate 1
Hydrate
Diethylhydroxylamine 5.0 g 8.0 g
Brightening Agent(WHITEX-4, product of
1.0 g 2.5 g
Sumitomo Chemical Co.)
Water to make 1000 ml 1000 ml
pH(adjusted with potassium hydroxide and
10.05 10.45
sulfuric acid)
Blixing Solution (The tank solution and the replenisher
were the same.)
Water 600 ml
Ammonium Thiosulfate (750 g/liter)
93 ml
Ammonium Sulfite 40 g
Ammonium Ethylenediaminetetraacetato/Iron(III)
55 g
Disodium Ethylenediaminetetraacetate
5 g
Nitric Acid (67%) 30 g
Water to make 1000 ml
pH (adjusted with acetic acid and aqueous ammonia)
5.8
Rinsing Solution (The tank solution and the replenisher
were the same.)
Sodium Chloroisocyanurate 0.02 g
Deionized Water (with electroconductivity of
1000 ml
5 .mu.S/cm or less)
pH 6.5
______________________________________
After the running processing as above above, each the above-mentioned 31
samples (Sample Nos. 101 to 131) was exposed for 1/10 second through a red
filter and then processed, using the processor that had been subjected to
the above-mentioned running processing. This is to check the
side-absorption characteristic of the colored cyan dye in each sample in a
short wavelength range.
The color density of each of the thus-processed samples was measured, using
a photodensitometer X-rite 310 Model (made by X-rite Co.) under the
instructed status-A condition. Precisely, the magenta density was measured
in each sample at the part that had been measured to have a cyan density
of 1.0, as the value to evaluate the cyan color hue in the same part. The
thus-measured value is shown in Table 2, indicating the cyan color hue of
each sample. The value indicates the proportion of the unnecessary
absorption in the green area to the main absorption of the formed dye. The
smaller the value, the better the cyan color hue.
Next, the pressure resistance of each sample was checked in the manner
mentioned below. Each sample was stored at 35.degree. C. and 55% RH for 10
days. Each of the fresh samples and the thus-stored samples was scratched
with a sapphire needle (its point had a radius of curvature of 0.03 mm) to
which a load of 2 g, 4 g or 8 g had been imparted, while the needle was
moved at a rate of 5 cm/sec on each sample. These samples were then
developed according to the process mentioned above, and the cyan stress
marks, if any, appeared on the processed samples were checked with the
naked eye. The degree of the stress marks, if any, was evaluated according
to the following ranks:
______________________________________
Evaluation: Degree of Stress Marks
______________________________________
xx: Clear stress marks appeared, when
a load of 2 g was imparted to the
needle.
x: Clear stress marks appeared, when
a load of 4 g was imparted to the
needle.
.smallcircle.:
Clear stress marks appeared, when
a load of 8 g was imparted to the
needle.
.circleincircle.:
No stress mark appeared, when a
load of 8 g was imparted to the
needle.
______________________________________
The sharpness of each sample was evaluated in the manner mentioned below.
Precisely, each sample was exposed to a red light, while a rectangular
pattern having a varying space frequency to have a difference in the
density of 0.5, that had been deposited on a glass support, was closely
attached thereto, and the thus-exposed sample was developed according to
the process mentioned above, using the processing solutions also mentioned
above. The exposure was effected in such a way that the background density
of each sample might be 1.0. The density of the thus-obtained rectangular
image was measured precisely with a microdensitometer, from which obtained
was the CTF value of each sample at a space frequency of 6.0 cycles/mm.
The value is an index of the sharpness of each sample.
The results of the above-mentioned tests are shown in Table 2. In these
tests, it was known that the maximum cyan color density of the samples
each containing the cyan coupler of the present invention was higher than
the comparative samples each containing the comparative coupler.
TABLE 2
__________________________________________________________________________
Support
Mean TiO.sub.2
Content Hue of Cyan
pH of Coated
Stress Marks
Sample No.
Code
(wt. %)
Cyan Coupler
Color Formed
Film Before Stored
After Stored
CTF
Remarks
__________________________________________________________________________
101 A 15.0 ExC 0.39 7.0 .circleincircle.
.circleincircle.
0.74
comparative
sample
102 A 15.0 ExC 0.39 6.5 .circleincircle.
.circleincircle.
0.75
comparative
sample
103 A 15.0 ExC 0.40 5.9 .circleincircle.
.circleincircle.
0.75
comparative
sample
104 D 12.5 ExC 0.39 7.0 .circleincircle.
.circleincircle.
0.76
comparative
sample
105 D 12.5 ExC 0.40 6.5 .circleincircle.
.circleincircle.
0.75
comparative
sample
106 D 12.5 ExC 0.40 5.9 .circleincircle.
.circleincircle.
0.75
comparative
sample
107 A 15.0 (11) 0.32 6.9 .circleincircle.
.largecircle.
0.75
comparative
sample
108 A 15.0 (11) 0.31 6.5 .circleincircle.
.circleincircle.
0.75
comparative
sample
109 A 15.0 (11) 0.32 5.8 .circleincircle.
.circleincircle.
0.76
comparative
sample
110 D 12.5 (11) 0.32 6.9 .largecircle.
X 0.77
comparative
sample
111 D 12.5 (11) 0.32 6.5 .circleincircle.
.circleincircle.
0.78
sample of the
invention
112 D 12.5 (11) 0.31 5.8 .circleincircle.
.circleincircle.
0.77
sample of the
invention
113 B 25.0 (11) 0.32 6.9 .circleincircle.
.largecircle.
0.80
comparative
sample
114 B 25.0 (11) 0.32 5.8 .circleincircle.
.circleincircle.
0.81
comparative
sample
115 C 14.7 (11) 0.31 6.9 .largecircle.
X 0.78
comparative
sample
116 C 14.7 (11) 0.32 5.8 .circleincircle.
.circleincircle.
0.79
sample of the
invention
117 E 15.0 (11) 0.32 6.9 .largecircle.
X 0.79
comparative
sample
118 E 15.0 (11) 0.32 6.2 .circleincircle.
.largecircle.
0.80
sample of the
invention
119 F 17.5 (11) 0.32 6.9 .largecircle.
XX 0.81
comparative
sample
120 F 17.5 (11) 0.32 5.8 .circleincircle.
.circleincircle.
0.81
sample of the
invention
121 G 25.0 (11) 0.32 6.9 .largecircle.
XX 0.83
comparative
sample
122 G 25.0 (11) 0.32 5.8 .circleincircle.
.circleincircle.
0.84
sample of the
invention
123 G 25.0 (27) 0.32 6.2 .circleincircle.
.largecircle.
0.84
sample of the
invention
124 G 25.0 (31) 0.31 6.3 .circleincircle.
.largecircle.
0.84
sample of the
invention
125 G 25.0 (35) 0.30 6.3 .circleincircle.
.circleincircle.
0.85
sample of the
invention
126 G 25.0 (36) 0.29 6.2 .circleincircle.
.largecircle.
0.84
sample of the
invention
127 G 25.0 (36) 0.29 5.9 .circleincircle.
.circleincircle.
0.85
sample of the
invention
128 H 30.0 (11) 0.32 6.9 .circleincircle.
XX 0.87
comparative
sample
129 H 30.0 (11) 0.33 5.8 .circleincircle.
.largecircle.
0.88
sample of the
invention
130 I 23.0 (11) 0.32 5.8 .circleincircle.
.circleincircle.
0.86
sample of the
invention
131 I 23.0 (35) 0.29 5.9 .circleincircle.
.circleincircle.
0.86
sample of the
invention
__________________________________________________________________________
From Table 2 above, it is known that the cyan couplers contained in the
samples of the present invention are better than the comparative coupler
(ExC) in that the the unnecessary absorption of the dyes formed from the
former is less than that of the dye formed from the latter.
Considering the sharpness of the images formed, it is known that the
samples having support D (having a mean TiO.sub.2 content of 12.5 wt. %)
are comparable to or better than those having support A (having a mean
TiO.sub.2 content of 15 wt. %) and that the samples having support E
(having a mean TiO.sub.2 content of 15 wt. %) are better than those having
support B (having a mean TiO.sub.2 content of 25 wt. %). This means that
the samples each having the support of the present invention may have a
reduced total amount of the white pigment to be in the waterproof resin
coat layer on the support while the sharpness of the images to be formed
is kept good. In addition, it is also noted that the samples having the
cyan coupler of the present invention have somewhat improved sharpness, as
compared with those having the comparative cyan coupler (compare Sample
Nos. 101 to 103 and Sample Nos. 107 to 109, and Sample Nos. 104 to 106 and
Sample Nos. 110 to 112). This effect is enhanced, when the cyan coupler
and the support are combined according to the present invention.
Therefore, the combination of the support and the coupler defined by the
present invention is effective in maintaining and improving the sharpness
of the images to be formed.
However, even though the coupler and the support are combined according to
the present invention, if the pH value of the film coated on the support
is higher than 6.5, the pressure resistance of the samples is worsened
after storage so that the samples cannot be put to practical use (see
Sample Nos. 110, 115, 117, 119, 121, 128).
Summarizing these results, it is known that the photographic material of
the present invention is excellent in that it gives an image having
excellent cyan color hue and that the content of the white pigment in the
support of the material may be reduced, while the sharpness of the image
formed is maintained or is even improved. In the technical level in the
prior art, the combination of the support and the coupler as defined by
the present invention resulted in the increase in the stress marks after
the photographic material was stored. According to the present invention,
however, the photographic material having the claimed combination of the
support and the coupler is free from the increase in the stress marks even
after stored.
EXAMPLE 2
Using a Fuji Color negative film, Super G400, pictures of a distant view of
a new town with a background of fresh green mountains were taken. This was
printed on each of Sample Nos. 103, 106, 109, 112, 114, 116, 118, 120,
122, 124, 126, 129 and 131 that had been prepared in Example 1. The color
prints thus obtained were sensually examined by 10 panelists, with respect
to the color hue and the sharpness of each image. The sensual evaluation
on the color hue and the sharpness of the images formed was effected
according to the point mentioned below, based on Sample No. 103, and the
total point of each sample was obtained.
______________________________________
Point: Evaluation
______________________________________
0: Much worse than Sample No. 103
1: Worse than Sample No. 103
2: Comparable to Sample No. 103
3: Better than Sample No. 103
4: Much better than Sample No. 103
______________________________________
The results are shown in Table 3.
TABLE 3
______________________________________
Point of Evaluation of Image Quality
Sample No.
Color Hue Sharpness Remarks
______________________________________
103 20 20 comparative
sample
106 21 24 comparative
sample
109 32 24 comparative
sample
112 33 30 sample of the
invention
114 32 32 sample of the
invention
116 32 28 sample of the
invention
118 32 30 sample of the
invention
120 33 34 sample of the
invention
122 34 37 sample of the
invention
124 36 40 sample of the
invention
126 37 40 sample of the
invention
129 34 42 sample of the
invention
131 38 42 sample of the
invention
______________________________________
From Table 3 above, it is known that the samples each having the coupler of
the present invention have larger points of the evaluation of the color
hue of the images formed and that the sharpness of the image reflects the
evaluation of the CTF value in Table 2 above. From these results, it is
obvious that the samples of the present invention give images having
better color hue and that the content of the white pigment in the
waterproof resin coat layer constituting the support of the sample of the
present invention may be reduced, while the visual sharpness of the image
to be formed is kept good, with the result that the cost for producing the
photographic material of the present invention may be reduced.
EXAMPLE 3
The samples prepared in Example 1 were processed according to the process
mentioned below, using the processing solutions also mentioned below. The
thus-processed samples were evaluated in the same manner as in Example 1,
by which the same results as in Example 1 were obtained.
______________________________________
Process for Color Development:
Amount of
Replenisher
Processing Step
Temperature
Time (*)
______________________________________
Color 38.5.degree. C.
45 sec 73 ml
Development
Blixation 38.5.degree. C.
45 sec 60 ml(**)
Rinsing 1 35 to 40.degree. C.
15 sec --
Rinsing 2 35 to 40.degree. C.
15 sec --
Rinsing 3 30 to 40.degree. C.
15 sec 360 ml
Drying 80.degree. C.
20 sec
______________________________________
(*)per m.sup.2 of the sample being processed.
(**)In addition to 60 ml mentioned above, 120 ml, per m.sup.2 of the
sample, of the carryover from the rinsing bath 1 was introduced into the
blixation bath.
Rinsing was effected by threetank countercurrent cascade system from 3 to
1.
Compositions of the processing solutions used above are mentioned below.
______________________________________
Tank Re-
Solution
plenisher
______________________________________
Color Developer
Water 800 ml 800 ml
Sodium 0.1 g 0.1 g
Triisopropylnaphthalene(.beta.)sulfonate
Ethylenediaminetetraacetic Acid
3.0 g 3.0 g
Disodium 1,2-Dihydroxybenzene-4,6-
0.5 g 0.5 g
disulfonate
Triethanolamine 12.0 g 12.0 g
Potassium Chloride 6.5 g --
Potassium Bromide 0.03 g --
Potassium Carbonate 27.0 g 27.0 g
Brightening Agent(WHITEX 4B, made by
1.0 g 1.0 g
Sumitomo Chemical Co.)
Sodium Sulfite 0.1 g 0.1 g
Disodium N,N- 10.0 g 13.0 g
bis(sulfonatoethyl)hydroxylamine
N-ethyl-N-(.beta.-methanesulfonamidoethyl)-3-
5.0 g 11.5 g
methyl-4-aminoaniline Sulfate
Water to make 1000 ml 1000 ml
pH (25.degree. C.) 10.00 11.00
Blix Solution
Water 600 ml 150 ml
Aqueous Solution of 93 ml 230 ml
Ammonium Thiosulfate (700 g/liter)
Ammonium Sulfite 40 g 100 g
Ammonium 55 g 135 g
Ethylenediaminetetraacetato/Iron(III)
Ethylenediaminetetraacetatic Acid
5 g 12.5 g
Nitric Acid (67%) 30 g 65 g
Water to make 1000 ml 1000 ml
pH (25.degree. C.), adjusted with acetic acid or
5.8 5.6
aqueous ammonia
Rinsing Solution:
Ion-exchanged Water (having calcium and magnesium
content of 3 ppm or less each).
______________________________________
EXAMPLE 4
The samples prepared in Example 1 were processed according to the process
mentioned below, using the processing solutions also mentioned below. The
thus-processed samples were evaluated in the same manner as in Example 1,
by which the same results as in Example 1 were obtained.
______________________________________
Process for Color Development:
Amount of
Replenisher
Processing Step
Temperature
Time (*)
______________________________________
Color 35.degree. C.
45 sec 161 ml
Development
Blixation 35.degree. C.
45 see 215 ml
Rinsing 1 35.degree. C.
20 sec --
Rinsing 2 35.degree. C.
20 sec --
Rinsing 3 35.degree. C.
20 sec --
Rinsing 4 35.degree. C.
20 sec 248 ml
Drying 80.degree. C.
60 sec
______________________________________
(*)per m.sup.2 of sample being processed.
(Rinsing was effected by fourtank countercurrent cascade system from 4 to
1.)
Compositions of the processing solutions used above are mentioned below.
______________________________________
Tank Re-
Color Developer Solution plenisher
______________________________________
Water 800 ml 800 ,
ml
Lithium Polystyrenesulfonate Solution (30
0.25 ml 0.25 ml
%)
1-Hydroxyethylidene-1,1-diphosphonic Acid
0.8 ml 0.8 ml
Solution (60%)
Lithium Sulfate Anhydride
2.7 g 2.7 g
Triethanolamine 8.0 g 8.0 g
Potassium Chloride 1.8 g --
Potassium Bromide 0.03 g 0.025
g
Diethylhydroxylamine 4.6 g 7.2 g
Glycine 5.2 g 8.1 g
Threonine 4.1 g 6.4 g
Potassium Carbonate 27 g 27 g
Potassium Sulfite 0.1 g 0.2 g
N-ethyl-N-(.beta.-methanesulfonamidoethyl)-3-
4.5 g 7.3 g
methyl-4-aminoaniline 3/2 Sulfate 1
Hydrate
Brightening Agent (4,4'-diaminostilbene
2.0 g 3.0 g
compound)
Water to make 1000 ml 1000 ml
pH, adjusted with potassium hydroxide and
10.12 10.70
sulfuric acid
______________________________________
Blixing Solution (The tank solution and the replenisher
were the same.)
Water 400 ml
Aqueous Solution of 100 ml
Ammonium Thiosulfate (750 wt/vol %)
Sodium Sulfite 17.0 g
Ammonium Ethylenediaminetetraacetato/Iron(III)
55.0 g
Disodium Ethylenediaminetetraacetate
5.0 g
Glacial Acetic Acid 9.0 g
Water to make 1000 ml
pH (adjusted with acetic acid and ammonia)
5.40
Rinsing Solution (The tank solution and the replenisher
were the same.)
1,2-Benzoisothiazolin-3-one 0.02 g
Polyvinyl Pyrrolidone 0.05 g
Water to make 1000 m
pH 7.0
______________________________________
EXAMPLE 5
The samples prepared in Example 1 were exposed in the manner mentioned
below and then processed in the same manner as in Example 1. The
thus-processed samples were evaluated in the same manner as in Example 1,
by which the same results as in Example 1 were obtained.
Exposure of Samples:
The samples were exposed by scanning exposure. As the light source, used
were a light of 473 nm that had been prepared by converting the wavelength
of a YAG solid laser (oscillating wavelength: 946 nm) combined with an
exciting light source of a semiconductor laser GaAlAs (oscillating
wavelength: 808.5 nm), using SHG crystals of KNbO.sub.3 ; a light of 532
nm that had been prepared by converting the wavelength of a YVO.sub.4
solid laser (oscillating wavelength: 1064 nm) combined with an exciting
light source of a semiconductor laser GaAlAs (oscillating wavelength:
808.7 nm), using SHG crystals of KTP; and a semiconductor laser AlGaInP
(TOLD 9211 Model, made by Toshiba Co.; oscillating wavelength: about 670
nm). The scanning exposure device used here was such that the laser rays
were successively applied to the color printing paper, which were being
moved in the direction vertical to the scanning direction, by the motion
of a rotary polyhedron. Using the device, the samples were exposed while
the quantity of light was varied, and the relation (D-logE) between the
density (D) of the processed sample and the quantity of light applied (E)
was obtained. The three laser rays each having a different wavelength as
mentioned above were modulated so as to vary the quantity of light from
each ray, using an external modulator, by which the amount of exposure of
each sample was controlled. The scanning exposure was effected at 400 dpi,
and the mean exposure time was about 5.times.10.sup.-8 seconds per one
pixel. Using a Peltier device, the temperatures of the semiconductor
lasers were kept constant in order to prevent the temperature-dependent
fluctuation of the quantity of light from each laser.
According to the present invention which has been explained in detail
hereinabove, there is provided a low-priced color photographic material
having a good coloring property, excellent color reproducibility and high
sharpness. As the material has sufficient pressure resistance, it has few
stress marks even after stored. The present invention also provides a
method for forming a color image, using the photographic material.
While the invention has been described in detail and with reference to
specific embodiments thereof, it will be apparent to one skilled in the
art that various changes and modifications can be made therein without
departing from the spirit and scope thereof.
Top